Reaction of olefin derivatives in the presence of metathesis catalysts

文档序号：1077966 发布日期：2020-10-16 浏览：22次中文

阅读说明：本技术 烯烃衍生物在复分解催化剂的存在下的反应 (Reaction of olefin derivatives in the presence of metathesis catalysts ) 是由 R·L·佩德尔森 A·M·约翰斯于 2019-02-11 设计创作，主要内容包括：本发明提供了一种用于合成麝香大环化合物的方法,所述方法包括接触承载Z-烯烃部分的易于获得的二烯原料,并且在第8族烯烃复分解催化剂的存在下进行闭环复分解反应。<Image he="831" wi="673" file="DDA0002629549350000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention provides a method for synthesizing musk macrocycles comprising contacting a readily available diene starting material bearing a Z-olefin moiety and conducting a ring closing metathesis reaction in the presence of a group 8 olefin metathesis catalyst.)

1. A process for the synthesis of a musk macrocyclic compound represented by formula (K)

The method comprises the following steps:

a) reacting an olefin represented by formula (G) in the presence of at least one group 8 metal olefin metathesis catalyst under conditions sufficient to form a metathesis product

With at least one metathesis reaction partner represented by formula (H),

wherein the at least one metathesis catalyst is represented by the structure of formula (4):

wherein:

R^1mis H or methyl;

OR^2mis a protected hydroxy group;

R^3mc being branched or straight chain₁-C₅An alkyl group;

x is 2, 3,4 or 5;

y is 5, 6, 7 or 8;

m is a group 8 transition metal;

L²is a neutral electron donor ligand;

n is 0 or 1;

m is 0, 1 or 2;

R^ais hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl;

X¹and X²Independently, an anionic ligand;

X⁵and Y⁵Independently C, CR^3AOr N; and X⁵Or Y⁵Only one of them may be C or CR^3A；

R^3AIs hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl;

q is a group having the structure- [ CR ]¹¹R¹²]_s-[CR¹³R¹⁴]_t-or- [ CR¹¹＝CR¹³]A diatomic bond of (a);

"s" and "t" are independently 1 or 2;

R³is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; and is

R⁴Is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl.

2. The olefin metathesis catalyst of claim 1, wherein:

m is Ru;

n is 0;

m is 0;

R^bis unsubstituted C₁-C₁₀Alkyl, substituted C₁-C₁₀Alkyl, unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl or substituted C₅-C₂₄An aryl group; or R^aAnd R^bLinked together to form a five or six membered heterocyclic ring having a sulfoxide group;

X¹and X²Independently is halogen;

R¹is hydrogen;

R²is unsubstituted phenyl, substituted phenyl, C₁-C₆Alkyl or substituted 1-propenyl; or R¹And R²Linked together to form an optionally substituted indenylene group;

X⁵and Y⁵Independently is N;

q is a group having the structure- [ CR ]¹¹R¹²]_s-[CR¹³R¹⁴]_tA diatomic bond of (a);

R¹¹、R¹²、R¹³and R¹⁴Independently is hydrogen;

"s" and "t" are independently 1;

R³is unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl or C substituted by up to three substituents selected from₅-C₂₄Aryl: unsubstituted C₁-C₂₀Alkyl, substituted C₁-C₂₀Alkyl, unsubstituted C₁-C₂₀Heteroalkyl, substituted C₁-C₂₀Heteroalkyl, unsubstituted C₅-C₂₄Aryl, substituted C₅-C₂₄Aryl, unsubstituted C₅-C₂₄Heteroaryl, substituted C₅-C₂₄Heteroaryl, unsubstituted C₆-C₂₄Aralkyl, substituted C₆-C₂₄Aralkyl, unsubstituted C₆-C₂₄Alkylaryl, substituted C₆-C₂₄Alkaryl and halide groups; and is

R⁴Is unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl or C substituted by up to three substituents selected from₅-C₂₄Aryl: unsubstituted C₁-C₂₀Alkyl, substituted C₁-C₂₀Alkyl, unsubstituted C₁-C₂₀Heteroalkyl, substituted C₁-C₂₀Heteroalkyl, unsubstituted C₅-C₂₄Aryl, substituted C₅-C₂₄Aryl, unsubstituted C₅-C₂₄Heteroaryl, substituted C₅-C₂₄Heteroaryl, unsubstituted C₆-C₂₄Aralkyl, substituted C₆-C₂₄Aralkyl, unsubstituted C₆-C₂₄Alkylaryl, substituted C₆-C₂₄Alkaryl and halide.

3. The olefin metathesis catalyst of claim 2, represented by the structure of formula (5),

wherein:

R¹is hydrogen;

R²is unsubstituted phenyl, substituted phenyl, C₁-C₆Alkyl or substituted 1-propenyl; or R¹And R²Linked together to form an optionally substituted indenylene group;

R^ais methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl or phenyl;

R^bis methyl, ethyl, n-butylPropyl, isopropyl, n-butyl, tert-butyl or phenyl; or R^aAnd R^bLinked together to form tetrahydrothiophene oxide having sulfoxide groups;

X¹and X²Independently Cl, Br, F or I;

R³is adamantyl, 2,4, 6-trimethylphenyl, 2, 6-diisopropylphenyl, 2-isopropyl-6-methylphenyl, 2-isopropyl-phenyl or 2-methyl-phenyl; and is

R⁴Is 2,4, 6-trimethylphenyl, 2, 6-diisopropylphenyl, 2-isopropyl-6-methylphenyl, 2-isopropyl-phenyl or 2-methyl-phenyl.

4. The olefin metathesis catalyst of claim 3 selected from the group consisting of:

5. the olefin metathesis catalyst of claim 1, wherein:

m is Ru;

n is 0;

m is 0;

X¹and X²Independently is halogen;

L¹Is composed of

X³And X⁴Independently is S or O;

R¹is hydrogen;

R²is unsubstituted phenyl, substituted phenyl, C₁-C₆Alkyl or substituted 1-propenyl;

X⁵and Y⁵Independently is N;

q is a group having the structure- [ CR ]¹¹R¹²]_s-[CR¹³R¹⁴]_tA diatomic bond of (a);

R¹¹、R¹²、R¹³and R¹⁴Independently is hydrogen;

"s" and "t" are independently 1;

R³is unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl or C substituted by up to three substituents selected from₅-C₂₄Aryl: unsubstituted C₁-C₂₀Alkyl, substituted C₁-C₂₀Alkyl, unsubstituted C₁-C₂₀Heteroalkyl, substituted C₁-C₂₀Heteroalkyl, unsubstituted C₅-C₂₄Aryl, substituted C₅-C₂₄Aryl, heteroaryl, and heteroaryl,Unsubstituted C₅-C₂₄Heteroaryl, substituted C₅-C₂₄Heteroaryl, unsubstituted C₆-C₂₄Aralkyl, substituted C₆-C₂₄Aralkyl, unsubstituted C₆-C₂₄Alkylaryl, substituted C₆-C₂₄Alkaryl and halide groups; and is

6. The olefin metathesis catalyst of claim 5, represented by the structure of formula (8)

Wherein:

R^ais methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or phenyl;

R^bis methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R^aAnd R^bLinked together to form a five or six membered heterocyclic ring having a sulfoxide group;

R³is adamantyl, 2,4, 6-trimethylphenyl, 2, 6-diisopropylphenyl, 2-methyl-6-tert-butylphenyl, 2-isopropyl-6-methylphenyl, 2-isopropyl-phenyl, 2, 6-diethylphenyl, 2-ethyl-6-methylphenyl, 2,4, 6-trifluorophenyl, 2, 6-difluorophenyl, 3, 5-di-tert-butylphenyl, 2, 4-dimethylphenyl or 2-methyl-phenyl;

R⁴is 2,4, 6-trimethylphenyl, 2, 6-diisopropylphenyl, 2-methyl-6-tert-butylphenyl, 2-isopropyl-6-methylphenyl, 2-isopropyl-phenyl, 2, 6-diethylphenyl, 2-ethyl-6-methylphenyl, 2,4, 6-trifluorophenyl, 2, 6-difluorophenyl, 3, 5-di-tert-butylphenyl, 2, 4-dimethylphenyl or 2-methyl-phenyl;

R¹is hydrogen, and R²Is unsubstituted phenyl, substituted phenyl, C₁-C₆Alkyl or substituted 1-propenyl; or R¹And R²Linked together to form an optionally substituted indenylene group;

R¹¹is hydrogen or methyl, R¹²Is hydrogen or methyl, R¹³Is hydrogen, and R¹⁴Is hydrogen;

R^xis methyl, hydrogen or Cl; r^yIs hydrogen; r^wIs hydrogen; r^zIs Cl, tert-butyl, hydrogen or phenyl; or R^xAnd R^yLinked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^wAnd R^zLinked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^yAnd R^wLinked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl.

7. The olefin metathesis catalyst of claim 6 selected from the group consisting of:

8. a process for synthesizing a musk macrocyclic compound represented by formula (a):

the process comprises ring-closing metathesis of a diene of formula (E) in the presence of at least one metathesis catalyst under conditions sufficient to form a metathesis product

Wherein:

R^eis H, methyl, ethyl or propyl;

p is 1,2, 3 or 4;

q is 4,5, 6 or 7;

wherein the at least one metathesis catalyst is represented by the structure of formula (4):

wherein:

m is a group 8 transition metal;

L²is a neutral electron donor ligand;

n is 0 or 1;

m is 0, 1 or 2;

R^ais hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl;

X¹and X²Independently, an anionic ligand;

R¹and R²Independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbonAn unsubstituted heteroatom-containing hydrocarbon group or a substituted heteroatom-containing hydrocarbon group; or R¹And R²Linked together to form an optionally substituted indenylene group;

X⁵and Y⁵Independently C, CR^3AOr N; and X⁵Or Y⁵Only one of them may be C or CR^3A；

R^3AIs hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl;

q is a group having the structure- [ CR ]¹¹R¹²]_s-[CR¹³R¹⁴]_t-or- [ CR¹¹＝CR¹³]A diatomic bond of (a);

"s" and "t" are independently 1 or 2;

R³is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; and is

R⁴Is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl.

9. The process of claim 8, wherein the olefin metathesis catalyst is represented by the structure of formula (5),

wherein:

R¹is hydrogen;

R²is unsubstituted phenyl, substituted phenyl, C₁-C₆Alkyl or substituted 1-propenyl; or R¹And R²Linked together to form an optionally substituted indenylene group;

R^ais methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl or phenyl;

R^bis methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl or phenyl; or R^aAnd R^bLinked together to form tetrahydrothiophene oxide having sulfoxide groups;

X¹and X²Independently Cl, Br, F or I;

R³is adamantyl, 2,4, 6-trimethylphenyl, 2, 6-diisopropylphenyl, 2-isopropyl-6-methylphenyl, 2-isopropyl-phenyl or 2-methyl-phenyl; and is

R⁴Is 2,4, 6-trimethylphenyl, 2, 6-diisopropylphenyl, 2-isopropyl-6-methylphenyl, 2-isopropyl-phenyl or 2-methyl-phenyl.

10. The process of claim 9, wherein the olefin metathesis catalyst is selected from the group consisting of:

11. the process of claim 8, wherein the olefin metathesis catalyst is represented by the structure of formula (8)

Wherein:

R^ais methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or phenyl;

R^bis methyl,Ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R^aAnd R^bLinked together to form a five or six membered heterocyclic ring having a sulfoxide group;

R¹is hydrogen, and R²Is unsubstituted phenyl, substituted phenyl, C₁-C₆Alkyl or substituted 1-propenyl; or R¹And R²Linked together to form an optionally substituted indenylene group;

R¹¹is hydrogen or methyl, R¹²Is hydrogen or methyl, R¹³Is hydrogen, and R¹⁴Is hydrogen;

12. The process of claim 11, wherein the olefin metathesis catalyst is selected from the group consisting of:

Background

Olefin metathesis has emerged as a valuable synthetic method for the formation of carbon-carbon double bonds since its discovery in the 50's of the 20 th century. Recent advances in organic synthesis and polymer synthesis applications have largely relied on the development of well-defined olefin metathesis catalysts.

Ruthenium metathesis catalyst technology has enabled the development of several research platforms, including: ring-opening metathesis polymerization (ROMP), ring-opening cross metathesis (ROCM), Cross Metathesis (CM), ring-closing metathesis (RCM).

In another embodiment, the present invention provides a method of synthesizing a macrocyclic compound for use in the fragrance industry.

The musk odour is probably the most widely recognised fragrance. Natural macrocyclic musk compounds are in fact ketones (of animal origin) and lactones (vegetable material). They are 15-membered ring systems or 17-membered ring systems. The type of odour is influenced by the size of the ring. Starting from 14 ring atoms, a slight musky smell is perceived. Compounds with 15-16 ring atoms exhibit a strong musky odour.

Macrocyclic musk compounds are expected to become increasingly important in the future, especially since many of them occur naturally and even synthetic representatives are highly similar to the natural counterparts. Furthermore, advances in synthetic chemistry have helped to reduce the price and will stimulate an increase in the use of such musk compounds.

Synthetic musk compounds can be divided into three main classes: aromatic nitro musk compounds, polycyclic musk compounds and macrocyclic musk compounds. Thus, macrocyclic musk compounds have gained increasing importance in recent years.

The synthesis of macrocyclic musk compounds is difficult and in many cases a multistep process. The economic significance of such compounds is still very limited due to the relatively high production costs. However, there is a great need in the perfume industry for a stable variety of these musk compounds.

There is a need for efficient processes for the preparation of cyclic compounds based on intermediate rings and especially on macrocycles having at least one keto group. The intermediate ring typically has 8 to 11 carbon atoms, rings higher than 12 carbon atoms are referred to as macrocycles, and macrocycle-based compounds are also referred to as macrocycles. Macrocyclic ketones, lactones and epoxides, as well as other functionalized macrocyclic compounds, are valuable fragrance chemicals in the fragrance industry. There is a need to create new synthetic routes for macrocyclic musk compounds of high value and value.

The present invention solves the problems of the prior art and provides for the efficient and high yield synthesis of macrocyclic musk compounds and their open-chain intermediates using cross-metathesis in the presence of a group 8 metal olefin metathesis catalyst.

The stereochemistry of olefins (E or Z) in these cyclic structures is often crucial for the biological activity of the molecule or its olfactory properties, and small amounts of impurities of other stereoisomers in chemical mixtures can significantly reduce their potency. It is particularly difficult to separate the E-and Z-isomers because their separation techniques are not general. Therefore, the process for producing stereochemically pure cyclic compounds is of crucial importance.

Controlling the olefin stereochemistry in RCM reactions can be difficult. When using common non-selective metathesis catalysts, selectivity is governed by the thermodynamic stability of the olefin product and can vary depending on the ring size and the position of the double bond.

In addition, macrocyclization reactions using RCM typically require high catalyst loadings. In these cases, removal of residual metals, the presence of which in the final product may be undesirable or potentially isomerize the product, may be difficult. For some applications, this requires further purification using additives or multiple chromatography columns, followed by treatment with charcoal.

Common macrocyclic musk compounds include musk lactones (9-and 7-musk lactones), norvalactone (nirvanolide), cyclopentadecenolide, melonic musk, musk ketene, cyclohexadecenone (velvione), dihydrocivetone, cyclopentadecanone, civetone and cyclohexadecenone (globanone).

The present invention provides a process for forming a macrocyclic musk compound, comprising the steps of: a first olefin and a second olefin are cross-metathesized in the presence of at least one group 8 metal olefin metathesis catalyst to form a cross-metathesis product, which is then cyclized to form the desired macrocyclic musk compound.

The macrocyclic musk compounds may be formed by ring-closing metathesis of dienes in the presence of at least one group 8 metal olefin metathesis catalyst. More particularly, the present invention relates to novel methods for obtaining musk macrocyclic compounds of the Z configuration via cross-metathesis reactions in the presence of at least one group 8 metal Z-stereoretentive olefin metathesis catalyst.

With the readily available diene feedstock carrying the Z-olefin moiety, the macrocyclization reaction produces products with significantly higher Z-selectivities with significantly shorter reaction times, higher yields and much lower catalyst loadings than previously reported systems. Macrolides ranging in size from twelve to seventeen membered rings with excellent Z-selectivity (95% - > 99% Z) were synthesized in moderate to high yields (68% -79% yield).

Disclosure of Invention

Macrocyclic compounds of musk

The present invention relates to a process for the preparation of cyclic compounds having at least eight carbon atoms and at least one keto group for use in the fragrance industry, comprising performing ring-closing metathesis in the presence of at least one group 8 metal olefin metathesis catalyst.

Ring-closing metathesis reactions are achieved using the catalysts of the present invention and have been shown to occur on a variety of substrates. The reaction was completed in dichloromethane at 40 ℃ under static vacuum (30mTorr) in 1 hour using a standard catalyst loading of 6 mole% typically used in macrocyclization reactions. Twelve-to seventeen-membered rings were synthesized all at high Z-selectivity (95% -99% Z) in moderate to high yields (68% -79% isolated yield). Yuzu lactone (Z) -oxacyclotridec-10-en-2-one is highly desirable for the fragrance industry and can be synthesized using ruthenium olefin metathesis catalysts more rapidly and selectively than previously reported. Larger macrolides (pentadecenyl to heptadecenyl) are synthesized in slightly higher yields than the smaller twelve to fourteen ring macrolides.

In summary, highly active ruthenium-based olefin metathesis catalysts are used to generate high-height Z-macrocycles (95% to 99% Z) from readily available diene substrates having Z-olefin moieties.

In another aspect, the macrocyclic musk compounds may be synthesized via ring-closing olefin metathesis of diolefins in the presence of at least one group 8 metal olefin metathesis catalyst.

In another embodiment, the ring-closing metathesis reaction product has a carbon-carbon double bond in the Z-configuration and is represented by the structure of formula (A):

wherein:

q is 1,2, 3, or 4; and

p is 4,5, 6 or 7.

In another embodiment, the ring-closing metathesis reaction product has a carbon-carbon double bond in the Z-configuration and is represented by the structure of formula (B):

wherein:

r is 1,2, 3 or 4; and

v is 4,5, 6 or 7.

In another embodiment, the ring-closing metathesis reaction product has a carbon-carbon double bond in the Z-configuration and is represented by the structure of formula (C):

wherein:

q^cis 1,2, 3 or 4; and

p^cis 4,5, 6 or 7.

In another embodiment, the ring-closing metathesis reaction product has a carbon-carbon double bond and is represented by the structure of formula (K):

wherein:

x is 2, 3,4 or 5;

y is 5, 6, 7 or 8.

In another aspect, the present invention provides a method of forming a macrocyclic musk compound, the method comprising the steps of: cross-metathesizing a first olefin and a second olefin in the presence of at least one group 8 metal olefin metathesis catalyst to form an intermediate of the first olefin and the second olefin, and cyclizing the intermediate to form a macrocyclic musk compound.

These and other aspects of the invention will be apparent to those skilled in the art from the following detailed description and examples. Furthermore, it should be understood that neither the embodiments nor examples of the invention described herein are to be construed as limiting.

Detailed Description

Unless otherwise specified, the invention is not limited to particular reactants, substituents, catalysts, reaction conditions, etc., as they may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

As used in the specification and the appended claims, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "an olefin" includes a single olefin as well as a combination or mixture of two or more olefins, reference to "a substituent" encompasses a single substituent as well as two or more substituents and the like.

As used in the specification and the appended claims, the terms "for example", "for instance", "such as" or "including" are intended to introduce examples that further illustrate more general subject matter. Unless otherwise indicated, these examples are provided solely to aid in the understanding of the present invention and are not meant to be limiting in any way.

In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined to have the following meanings:

as used herein, the term "alkyl" generally refers to a straight, branched, or cyclic saturated hydrocarbon group, but not necessarily containing 1 to 30 carbon atoms, typically containing 1 to 24 carbon atoms, typically 1 to 12 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, octyl, decyl, and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl, and the like. The term "lower alkyl" refers to an alkyl group having 1 to 6 carbon atoms, and the specific term "cycloalkyl" refers to a cyclic alkyl group typically having 3 to 12, or 4 to 12, or 3 to 10, or 3 to 8 carbon atoms. The term "substituted alkyl" refers to an alkyl group substituted with one or more substituent groups, and the terms "heteroatom-containing alkyl" and "heteroalkyl" refer to an alkyl group in which at least one carbon atom is replaced with a heteroatom. The terms "alkyl" and "lower alkyl" if not otherwise indicated include straight-chain, branched-chain, cyclic, unsubstituted, substituted and/or heteroatom-containing alkyl and lower alkyl, respectively.

As used herein, the term "alkylene" refers to a divalent straight, branched, or cyclic alkyl group, wherein "alkyl" is as defined herein.

As used herein, the term "alkenyl" refers to a straight, branched, or cyclic hydrocarbon group having 2 to 30 carbon atoms containing at least one double bond, such as ethenyl, n-propenyl, iso-propenyl, n-butenyl, iso-butenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, tetracenyl, and the like. Generally, an "alkenyl" group herein contains 2 to 24 carbon atoms, and typically an "alkenyl" group herein contains 2 to 12 carbon atoms. The term "lower alkenyl" refers to an "alkenyl" group having 2 to 6 carbon atoms, and the particular term "cycloalkenyl" refers to a cyclic "alkenyl" group typically having 5 to 8 carbon atoms. The term "substituted alkenyl" refers to "alkenyl" substituted with one or more substituent groups, and the terms "heteroatom-containing alkenyl" and "heteroalkenyl" refer to "alkenyl" in which at least one carbon atom is replaced with a heteroatom. The terms "alkenyl" and "lower alkenyl", if not otherwise indicated, include straight-chain, branched-chain, cyclic, unsubstituted, substituted and/or heteroatom-containing "alkenyl" and lower "alkenyl", respectively. The term "alkenyl" is used interchangeably with the term "alkene" herein.

As used herein, the term "alkenylene" refers to a divalent straight, branched, or cyclic alkenyl group, wherein "alkenyl" is as defined herein.

As used herein, the term "alkynyl" refers to a straight or branched chain hydrocarbon group having 2 to 30 carbon atoms containing at least one triple bond, such as ethynyl, n-propynyl, and the like. Generally, an "alkynyl" group herein contains 2 to 24 carbon atoms; typically, an "alkynyl" group as described herein contains from 2 to 12 carbon atoms. The term "lower alkynyl" refers to an "alkynyl" group having 2 to 6 carbon atoms. The term "substituted alkynyl" refers to "alkynyl" substituted with one or more substituent groups, and the terms "heteroatom-containing alkynyl" and "heteroalkynyl" refer to "alkynyl" in which at least one carbon atom is replaced with a heteroatom. The terms "alkynyl" and "lower alkynyl" include straight-chain, branched-chain, unsubstituted, substituted and/or heteroatom-containing "alkynyl" and lower "alkynyl", respectively, if not otherwise indicated.

As used herein, the term "alkoxy" refers to an alkyl group bonded through a single terminal ether linkage; that is, an "alkoxy" group can be represented as-O-alkyl, where alkyl is as defined herein. "lower alkoxy" group refers to an alkoxy group containing 1 to 6 carbon atoms. Similarly, "alkenyloxy" and "lower alkenyloxy" refer to alkenyl and lower alkenyl groups, respectively, bonded through a single terminal ether linkage, and "alkynyloxy" and "lower alkynyloxy" refer to alkynyl and lower alkynyl groups, respectively, bonded through a single terminal ether linkage.

As used herein, and unless otherwise indicated, the term "aryl" refers to an aromatic substituent containing a single aromatic ring or multiple aromatic rings that are fused together, directly linked, or indirectly linked (such that different aromatic rings are bonded to a common group such as a methylene or ethylene moiety). An "aryl" group contains 5 to 30 carbon atoms, typically an "aryl" group contains 5 to 20 carbon atoms; and typically, an "aryl" group contains 5 to 14 carbon atoms. Exemplary "aryl" groups contain one aromatic ring or two fused or linked aromatic rings, such as phenyl, naphthyl, biphenyl, diphenyl ether, diphenylamine, benzophenone, and the like. "substituted aryl" refers to an aryl moiety substituted with one or more substituent groups; for example, 2,4, 6-trimethylphenyl (i.e., mesityl or Mes), 2-methyl-phenyl, 2, 6-di-isopropylphenyl (i.e., DIPP or DIPP), 2-isopropyl-phenyl (i.e., IPP or IPP), 2-isopropyl-6-methylphenyl (i.e., MIPP or MIPP). The terms "heteroatom-containing aryl" and "heteroaryl" refer to an "aryl" substituent in which at least one carbon atom is replaced with a heteroatom, as will be described in further detail below.

As used herein, the term "aryloxy" refers to an aryl group bonded through a single terminal ether linkage, wherein "aryl" is as defined herein. An "aryloxy" group can be represented as-O-aryl, where aryl is as defined herein. Preferred "aryloxy" groups contain 5 to 24 carbon atoms, and particularly preferred "aryloxy" groups contain 5 to 14 carbon atoms. Examples of "aryloxy" groups include, but are not limited to, phenoxy, o-halo-phenoxy, m-halo-phenoxy, p-halo-phenoxy, o-methoxy-phenoxy, m-methoxy-phenoxy, p-methoxy-phenoxy, 2, 4-dimethoxy-phenoxy, 3,4, 5-trimethoxy-phenoxy, and the like.

The term "alkaryl" refers to an aryl group having an alkyl substituent, and the term "aralkyl" refers to an alkyl group having an aryl substituent, wherein "aryl" and "alkyl" are defined herein. The "alkaryl" and "aralkyl" groups contain from 6 to 30 carbon atoms; generally, "alkaryl" and "aralkyl" groups contain from 6 to 20 carbon atoms; and generally, "alkaryl" and "aralkyl" groups contain from 6 to 16 carbon atoms. "alkaryl" groups include, for example, p-methylphenyl, 2, 4-dimethylphenyl, p-cyclohexylphenyl, 2, 7-dimethylnaphthyl, 7-cyclooctylphenyl, 3-ethyl-cyclopenta-1, 4-diene, and the like. Examples of "aralkyl" groups include, but are not limited to, benzyl, 2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl, 4-benzylcyclohexylmethyl, and the like. The terms "alkylaryloxy" and "aralkyloxy" refer to a substituent of the formula — OR, wherein R is "alkylaryl" OR "arylalkyl," respectively, as defined herein.

The term "acyl" refers to a substituent having the formula- (CO) -alkyl, - (CO) -aryl, or- (CO) -aralkyl, and the term "acyloxy" refers to a substituent having the formula-O (CO) -alkyl, -O (CO) -aryl, or-O (CO) -aralkyl, wherein "alkyl", "aryl", and "aralkyl" are as defined herein.

The terms "cyclic" and "ring" refer to an alicyclic or aromatic group, which may or may not be substituted and/or contain heteroatoms, and which may be monocyclic, bicyclic, or polycyclic. The term "cycloaliphatic," as used in the conventional sense, refers to an aliphatic cyclic moiety, as opposed to an aromatic cyclic moiety, which may be monocyclic, bicyclic, or polycyclic.

The terms "halo", "halogen" and "halide" are used in their conventional sense to refer to chloro, bromo, fluoro or iodo substituents.

The term "hydrocarbyl" refers to a monovalent "hydrocarbyl" moiety containing 1 to 30 carbon atoms, typically 1 to 24 carbon atoms, specifically 1 to 12 carbon atoms, and includes straight, branched, cyclic, saturated, and unsaturated species such as alkyl groups, alkenyl groups, aryl groups, and the like. The term "lower hydrocarbyl" refers to "hydrocarbyl" groups having 1 to 6 carbon atoms, typically 1 to 4 carbon atoms, and the term "hydrocarbylene" refers to a divalent "hydrocarbyl" moiety containing 1 to 30 carbon atoms, typically 1 to 24 carbon atoms, specifically 1 to 12 carbon atoms, including straight, branched, cyclic, saturated and unsaturated species. The term "lower hydrocarbylene" refers to a "hydrocarbylene" group having from 1 to 6 carbon atoms. "substituted hydrocarbyl" refers to "hydrocarbyl" substituted with one or more substituent groups, and the terms "heteroatom-containing hydrocarbyl" and "heterohydrocarbyl" refer to hydrocarbyl in which at least one carbon atom is replaced with a heteroatom. Similarly, "substituted hydrocarbylene" refers to "hydrocarbylene" substituted with one or more substituent groups, and the terms "heteroatom-containing hydrocarbylene" and "heterohydrocarbylene" refer to "hydrocarbylene" in which at least one carbon atom is replaced with a heteroatom. Unless otherwise indicated, the terms "hydrocarbyl" and "hydrocarbylene" will be understood to include substituted and/or heteroatom-containing "hydrocarbyl" and "hydrocarbylene" moieties, respectively.

The term "heteroatom-containing" as in "heteroatom-containing hydrocarbyl group" refers to a hydrocarbon molecule or a fragment of a hydrocarbyl molecule in which one or more carbon atoms are replaced by an atom other than carbon, such as nitrogen, oxygen, sulfur, phosphorus, or silicon, typically nitrogen, oxygen, or sulfur. Similarly, the term "heteroalkyl" refers to a heteroatom-containing alkyl substituent, the term "heterocycle" refers to a heteroatom-containing cyclic substituent, and the terms "heteroaryl" and "heteroaromatic" refer to a heteroatom-containing "aryl" and "aromatic" substituent, respectively, and the like. It should be noted that the "heterocyclic" group or compound may or may not be aromatic, and it should also be noted that the "heterocyclic" may be monocyclic, bicyclic, or polycyclic, as described above with respect to the term "aryl". Examples of heteroaryl groups include alkoxyaryl, alkylsulfanyl-substituted alkyl, N-alkylated aminoalkyl, and the like. Examples of heteroaryl substituents include pyrrolyl, pyrrolidinyl, pyridyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl, 1,2, 4-triazolyl, tetrazolyl, and the like.

By "substituted" as in "substituted hydrocarbyl", "substituted alkyl", "substituted aryl", and the like, as incidentally mentioned in some of the foregoing definitions, it is meant that in the hydrocarbyl, alkyl, aryl, or other moiety, at least one hydrogen atom bonded to a carbon (or other) atom is replaced with one or more non-hydrogen substituents. Examples of such substituents include, but are not limited to: functional groups referred to herein as "Fn", such as halo, hydroxy, mercapto, C₁-C₂₄Alkoxy radical, C₂-C₂₄Alkenyloxy radical, C₂-C₂₄Alkynyloxy, C₅-C₂₄Aryloxy radical, C₆-C₂₄Aralkyloxy radical, C₆-C₂₄Alkaryloxy, acyl (including C)₂-C₂₄Alkylcarbonyl (-CO-alkyl) and C₆-C₂₄Arylcarbonyl (-CO-aryl)), acyloxy (-O-acyl, including C)₂-C₂₄Alkylcarbonyloxy (-O-CO-alkyl) and C₆-C₂₄Arylcarbonyloxy (-O-CO-aryl)), C₂-C₂₄Alkoxycarbonyl (- (CO) -O-alkyl), C₆-C₂₄Aryloxycarbonyl (- (CO) -O-aryl), halocarbonyl (- (CO) -X wherein X is halo), C₂-C₂₄Alkylcarbonate (-O- (CO) -O-alkyl), C₆-C₂₄Arylcarbonate (-O- (CO) -O-aryl), carboxyl (-COOH), carboxylate (-COO)^-) Carbamoyl (- (CO) -NH)₂) Mono- (C)₁-C₂₄Alkyl) -substituted carbamoyl (- (CO) -NH (C)₁-C₂₄Alkyl)), di- (C)₁-C₂₄Alkyl) -substituted carbamoyl (- (CO) -N (C)₁-C₂₄Alkyl radical)₂) Mono- (C)₅-C₂₄Aryl) -substituted carbamoyl (- (CO) -NH-aryl), di- (C)₅-C₂₄Aryl) -substituted carbamoyl (- (CO) -N (C)₅-C₂₄Aryl radical)₂) Thiocarbamoyl (- (CS) -NH)₂) Mono- (C)₁-C₂₄Alkyl) -substituted thiocarbamoyl (- (CS) -NH (C)₁-C₂₄Alkyl)), di- (C)₁-C₂₄Alkyl) -substituted thiocarbamoyl (- (CS) -N (C)₁-C₂₄Alkyl radical)₂) Mono- (C)₅-C₂₄Aryl) -substituted thiocarbamoyl (- (CS) -NH-aryl), bis- (C)₅-C₂₄Aryl) -substituted thiocarbamoyl (- (CS) -N (C)₅-C₂₄Aryl radical)₂) Ureido (-NH- (CO) -NH)₂) Cyano (-C.ident.N), cyanato (-O-C.ident.N), thiocyanate (-S-C.ident.N), formyl (- (CO) -H), thiocarbonyl (- (CS) -H), amino (-NH-H)₂) Mono- (C)₁-C₂₄Alkyl) -substituted amino, di- (C)₁-C₂₄Alkyl) -substituted amino, mono- (C)₅-C₂₄Aryl) -substituted amino, di- (C)₅-C₂₄Aryl) -substitutedAmino group(s), (C)₁-C₂₄Alkyl) (C₅-C₂₄Aryl) -substituted amino, (C)₂-C₂₄Alkyl) -amido (-NH- (CO) -alkyl), (C)₆-C₂₄Aryl) -amido (-NH- (CO) -aryl), imino (-CR ═ NH, where R is hydrogen, C₁-C₂₄Alkyl radical, C₅-C₂₄Aryl radical, C₆-C₂₄Alkylaryl group, C₆-C₂₄Aralkyl, etc.), (C₂-C₂₀Alkyl) -imino (-CR ═ N (alkyl), where R is hydrogen, C₁-C₂₄Alkyl radical, C₅-C₂₄Aryl radical, C₆-C₂₄Alkylaryl group, C₆-C₂₄Aralkyl, etc.), arylimino (-CR ═ N (aryl), where R is hydrogen, C₁-C₂₀Alkyl radical, C₅-C₂₄Aryl radical, C₆-C₂₄Alkylaryl group, C₆-C₂₄Aralkyl, etc.), nitro (-NO)₂) Nitroso group (-NO), sulfo group (-SO)₂-OH), sulfonate (-SO)₂-O^-)、(C₁-C₂₄Alkyl) -sulfanyl (-S-alkyl; also referred to as "alkylthio"), (C)₅-C₂₄Aryl) -sulfanyl (-S-aryl; also known as "arylthio"), (C)₁-C₂₄Alkyl-sulfinyl (- (SO) -alkyl), (C)₅-C₂₄Aryl-sulfinyl (- (SO) -aryl), (C)₁-C₂₄Alkyl) -sulfonyl (-SO₂Alkyl), mono- (C)₁-C₂₄Alkyl) -aminosulfonyl (-SO₂-N (H) alkyl), di- (C)₁-C₂₄Alkyl) -aminosulfonyl (-SO₂-N (alkyl)₂)、(C₅-C₂₄Aryl) -sulfonyl (-SO)₂Aryl), boron (-BH)₂) Boron-dioxy (-B (OH)₂) Boronato (boronato) (-B (OR))₂Wherein R is alkyl or other hydrocarbyl group, phosphono (-P (O) (OH)₂) Phosphonoxy (-P (O) (-) (O))^-)₂) Phosphinic acid ester group (phosphinato) (-P (O) (-O)^-) Phosphorus oxide (-PO), phosphorus oxide₂) And phosphino (-PH)₂) (ii) a And a hydrocarbyl moiety C₁-C₂₄Alkyl (preferably C)₁-C₁₂Alkyl, more preferably C₁-C₆Alkyl group), C₂-C₂₄Alkenyl (preferably C)₂-C₁₂Alkenyl, more preferably C₂-C₆Alkenyl), C₂-C₂₄Alkynyl (preferably C)₂-C₁₂Alkynyl, more preferably C₂-C₆Alkynyl), C₅-C₂₄Aryl (preferably C)₅-C₁₄Aryl group), C₆-C₂₄Alkylaryl (preferably C)₆-C₁₆Alkaryl), and C₆-C₂₄Aralkyl (preferably C)₆-C₁₆Aralkyl).

The term "NHC" ligand refers to an N-heterocyclic carbene ligand.

The term "CAAC" ligand refers to a cyclic alkylamino carbene ligand, also known as a "Bertrand-type ligand".

Functional groups such as ethers, esters, hydroxyl, carbonates may be protected in cases where the functional group interferes with the olefin metathesis catalyst, and any of the protecting groups commonly used in the art may be employed. Acceptable protecting Groups can be found, for example, in Greene et al, Protective Groups in Organic Synthesis, 4 th edition (published by John Wiley & Sons, Inc., Hobock, N.J., 2007).

The olefin geometry described in this application may have an E-configuration, or a Z-configuration, or a mixture of E-and Z-configurations. Applicant has achieved through the use of wave-shaped keysRepresents a mixture of double bond isomers. For example, as represented herein, a structureIllustrating the E-configuration

Or in the Z-configuration

OrMay represent a mixture of E-configuration and Z-configuration. Suitable ether protecting groups include branched or unbranched alkyl moieties containing from 1 to 5 carbon atoms, such as methyl, ethyl, propyl, isopropyl, tert-butyl or tert-pentyl.

Suitable ester protecting groups include-c (o) R (where R ═ hydrogen) or branched or unbranched alkyl moieties containing 1 to 7 carbon atoms, such as methyl, ethyl, propyl, isopropyl, tert-butyl or tert-pentyl.

Suitable silyl ether protecting groups include-Si (R)₃(ii) a Where R is a branched or unbranched alkyl moiety, which may include methyl, ethyl, propyl and tert-butyl.

Suitable carbonate protecting groups include-C (O) OR, where R is a branched OR unbranched alkyl moiety, such as methyl, ethyl, OR propyl.

By "sulfoxide group" is meant- [ S (O) ] -.

By "functionalized" as in "functionalized hydrocarbyl," "functionalized alkyl," "functionalized olefin," "functionalized cyclic olefin," and the like, is meant that in the hydrocarbyl, alkyl, olefin, cyclic olefin, or other moiety, at least one hydrogen atom bonded to a carbon (or other) atom is replaced with one or more functional groups such as those described above. The term "functional group" is meant to include any functional material suitable for the purposes described herein. In particular, as used herein, a functional group must have the ability to react or bond with a corresponding functional group on the surface of a substrate.

In addition, if permitted by a particular functional group, the functional group can be further substituted with one or more additional functional groups or one or more hydrocarbyl moieties such as those specifically enumerated herein. Similarly, the hydrocarbyl moieties described herein may be further substituted with one or more functional groups or additional hydrocarbyl moieties such as those specifically enumerated.

"optional" or "optionally" means that the subsequently described circumstance may or may not occur, such that the description includes instances where the circumstance occurs and instances where it does not. For example, the phrase "optionally substituted" means that a non-hydrogen substituent may or may not be present on a given atom, and thus, the description includes structures wherein a non-hydrogen substituent is present and structures wherein a non-hydrogen substituent is not present.

Group 8 metal olefin metathesis catalysts

The group 8 metal olefin metathesis catalyst of the invention is represented by the general structure of formula (1)

Wherein:

m is a group 8 transition metal; typically, M is ruthenium or osmium; typically, M is ruthenium;

L¹and L²Independently a neutral electron donor ligand;

n is 0 or 1; typically, n is 0;

m is 0, 1 or 2; typically, m is 0;

R^ais hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; in general, R^aIs unsubstituted C₁-C₁₀Alkyl, substituted C₁-C₁₀Alkyl, unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl or substituted C₅-C₂₄An aryl group; in general, R^aIs methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or phenyl;

R^bis hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; in general, R^bIs unsubstituted C₁-C₁₀Alkyl, substituted C₁-C₁₀Alkyl, unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl or substituted C₅-C₂₄An aryl group; in general, R^bIs methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexylOr phenyl; or R^aAnd R^bAre linked together to form a polymer having a sulfoxide group [ -S (O) -]A five-or six-membered heterocyclic ring of (a);

X¹and X²Independently, an anionic ligand; generally, X¹And X²Independently halogen, trifluoroacetate, perfluorophenol or nitrate; in general, X¹And X²Independently Cl, Br, I or F; and is

R¹And R²Independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; in general, R¹Is hydrogen, and R²Is unsubstituted phenyl, substituted phenyl, C₁-C₆Alkyl or substituted 1-propenyl; or R¹And R²Linked together to form an optionally substituted indenylene.

In some embodiments of formula (1),

is composed of

Wherein:

M、X¹and X²As defined herein;

X³and X⁴Independently is O or S; and is

R^x、R^y、R^wAnd R^zIndependently hydrogen, halogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R^xAnd R^yLinked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^wAnd R^zLinked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^yAnd R^wLinked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl.

The group 8 metal olefin metathesis catalyst used in the present invention may be represented by the structure of formula (2):

wherein:

m is a group 8 transition metal; typically, M is ruthenium or osmium; typically, M is ruthenium;

L¹and L²Independently a neutral electron donor ligand;

n is 0 or 1; typically, n is 0;

m is 0, 1 or 2; typically, m is 0;

R^bis hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; in general, R^bIs unsubstituted C₁-C₁₀Alkyl, substituted C₁-C₁₀Alkyl, unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl or substituted C₅-C₂₄An aryl group; in general, R^bIs methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R^aAnd R^bLinked together to form a five or six membered heterocyclic ring having a sulfoxide group;

R¹and R²Independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heterolepticAn atomic hydrocarbyl or substituted heteroatom-containing hydrocarbyl; in general, R¹Is hydrogen, and R²Is unsubstituted phenyl, substituted phenyl, C₁-C₆Alkyl or substituted 1-propenyl; or R¹And R²Linked together to form an optionally substituted indenylene group;

X³and X⁴Independently is O or S; in general, X³And X⁴Independently is S; and

R^x、R^y、R^wand R^zIndependently hydrogen, halogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; in general, R^x、R^y、R^wAnd R^zIndependently hydrogen, halogen, unsubstituted C₁-C₁₀Alkyl, substituted C₁-C₁₀Alkyl, unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl or substituted C₅-C₂₄An aryl group; in general, R^x、R^y、R^wAnd R^zIndependently is C₁-C₆Alkyl, hydrogen, unsubstituted phenyl, substituted phenyl or halogen; or R^xAnd R^yLinked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^wAnd R^zLinked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^yAnd R^wLinked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl.

The group 8 metal olefin metathesis catalyst used in the present invention is represented by the structure of formula (3),

wherein:

m is a group 8 transition metal; typically, M is ruthenium or osmium; typically, M is ruthenium;

L²is a neutral electron donor ligand;

n is 0 or 1; typically, n is 0;

m is 0, 1 or 2; typically, m is 0;

R^bis hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; in general, R^bIs unsubstituted C₁-C₁₀Alkyl, substituted C₁-C₁₀Alkyl, unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl or substituted C₅-C₂₄An aryl group; in general, R^bIs methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R^aAnd R^bLinked together to form a five or six membered heterocyclic ring having a sulfoxide group;

X¹and X²Independently, an anionic ligand; generally, X¹And X²Independently halogen, trifluoroacetate, perfluorophenol or nitrate; in general, X¹And X²Independently Cl, Br, I or F;

R¹and R²Independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; in general, R¹Is hydrogen, and R²Is unsubstituted phenyl, substituted phenyl, C₁-C₆Alkyl or substituted 1-propenyl; or R¹And R²Linked together to form an optionally substituted indenylene group;

X⁵and Y⁵Independently C, CR^3AN, O, S or P; x⁵Or Y⁵Only one of them may be C or CR^3A(ii) a In general, X⁵And Y⁵Independently is N;

Q¹、Q²、R³、R^3Aand R⁴Independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; generally speaking, Q¹、Q²、R³、R^3AAnd R⁴Is optionally attached to X via a linking group such as unsubstituted hydrocarbylene, substituted hydrocarbylene, unsubstituted heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, or- (CO) -⁵Or Y⁵(ii) a Generally, Q¹、Q²、R³、R^3AAnd R⁴Directly connected to X⁵Or Y⁵(ii) a And is

When X is present⁵When is O or S, p is 0; when X is present⁵Is N, P or CR^3AWhen p is 1; and when X⁵When is C, p is 2; when Y is⁵Q is 0 when O or S is contained; when Y is⁵Is N, P or CR^3AWhen q is 1; and when X⁵When it is C, q is 2.

The group 8 metal olefin metathesis catalyst used in the present invention is represented by the structure of formula (4):

wherein:

m is a group 8 transition metal; typically, M is ruthenium or osmium; typically, M is ruthenium;

n is 0 or 1; typically, n is 0;

m is 0, 1 or 2; typically, m is 0;

R^ais hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substitutedA heteroatom-containing hydrocarbon group; in general, R^aIs unsubstituted C₁-C₁₀Alkyl, substituted C₁-C₁₀Alkyl, unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl or substituted C₅-C₂₄An aryl group; in general, R^aIs methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or phenyl;

or R^aAnd R^bLinked together to form a five or six membered heterocyclic ring having a sulfoxide group;

X¹and X²Independently, an anionic ligand; generally, X¹And X²Independently halogen, trifluoroacetate, perfluorophenol or nitrate; in general, X¹And X²Independently Cl, Br, I or F;

X⁵and Y⁵Independently C, CR^3AOr N; x⁵Or Y⁵Only one of them may be C or CR^3A(ii) a In general, X⁵And Y⁵Independently is N;

R^3Ais hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl;

q is a linking group, typically unsubstituted hydrocarbylene, substituted hydrocarbylene, unsubstituted heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene; generally, Q is a compound having the structure- [ CR ]¹¹R¹²]_s-[CR¹³R¹⁴]_t-or- [ CR¹¹＝CR¹³]A diatomic bond of (a); typically, Q is- [ CR ]¹¹R¹²]_s-[CR¹³R¹⁴]_t-, wherein R¹¹、R¹²、R¹³And R¹⁴Independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; in general, R¹¹、R¹²、R¹³And R¹⁴Independently hydrogen, unsubstituted C₁-C₁₂Alkyl, substituted C₁-C₁₂Alkyl, unsubstituted C₁-C₁₂Heteroalkyl, substituted C₁-C₁₂Heteroalkyl, unsubstituted C₅-C₁₄Aryl or substituted C₅-C₁₄An aryl group;

"s" and "t" are independently 1 or 2; typically, "s" and "t" are independently 1; or R¹¹、R¹²、R¹³And R¹⁴Optionally joined together to form a substituted or unsubstituted, saturated or unsaturated ring structure;

R³is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; in general, R³Is unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted (C)₅-C₂₄Aryl), substituted with up to three substituents selected from the group consisting of₅-C₂₄Aryl): unsubstituted C₁-C₂₀Alkyl, substituted C₁-C₂₀Alkyl, unsubstituted C₁-C₂₀Heteroalkyl, substituted C₁-C₂₀Heteroalkyl, unsubstituted C₅-C₂₄Aryl, substituted C₅-C₂₄Aryl, unsubstituted C₅-C₂₄Heteroaryl, substituted C₅-C₂₄Heteroaryl, unsubstituted C₆-C₂₄Aralkyl, substituted C₆-C₂₄Aralkyl, unsubstituted C₆-C₂₄Alkylaryl, substituted C₆-C₂₄Alkaryl and halide groups; in general, R³Is adamantyl, 2,4, 6-trimethylphenyl, 2, 6-diisopropylphenyl, 2-methyl-6-tert-butylphenyl, 2-isopropyl-6-methylphenyl, 2-isopropyl-phenyl, 2, 6-diethylphenyl, 2-ethyl-6-methylphenyl, 2,4, 6-trifluorophenyl, 3, 5-di-tert-butylphenyl, 2, 4-dimethylphenyl, 2, 6-difluorophenyl, 2-fluoro-6-methylphenyl or 2-methyl-phenyl; and is

R⁴Is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; in general, R⁴Is unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted (C)₅-C₂₄Aryl) or (C) substituted by up to three substituents selected from₅-C₂₄Aryl): unsubstituted C₁-C₂₀Alkyl, substituted C₁-C₂₀Alkyl, unsubstituted C₁-C₂₀Heteroalkyl, substituted C₁-C₂₀Heteroalkyl, unsubstituted C₅-C₂₄Aryl, substituted C₅-C₂₄Aryl, unsubstituted C₅-C₂₄Heteroaryl, substituted C₅-C₂₄Heteroaryl, unsubstituted C₆-C₂₄Aralkyl, substituted C₆-C₂₄Aralkyl, unsubstituted C₆-C₂₄Alkylaryl, substituted C₆-C₂₄Alkaryl and halide groups; in general, R⁴Is 2,4, 6-trimethylphenyl, 2, 6-diisopropylphenyl, 2-methyl-6-tert-butylphenyl, 2-isopropyl-6-methylphenyl, 2-iso-propylPropyl-phenyl, 2, 6-diethylphenyl, 2-ethyl-6-methylphenyl, 2,4, 6-trifluorophenyl, 3, 5-di-tert-butylphenyl, 2, 4-dimethylphenyl, 2, 6-difluorophenyl, 2-fluoro-6-methylphenyl or 2-methyl-phenyl; or when X is⁵Is CR^3AWhen R is^3AAnd R⁴May form, together with the carbon atom to which they are attached, a five-to ten-membered cycloalkyl or heterocyclic ring.

In some embodiments of formula (4),

is composed of

Wherein: x¹、X²、X³、X⁴、M、R^x、R^y、R^wAnd R^zAs defined herein.

When Q is- [ CR ]¹¹R¹²]_s-[CR¹³R¹⁴]_t-, s is 1, t is 1, and R is¹¹、R¹²、R¹³And R¹⁴Independently hydrogen, and M is ruthenium, the olefin metathesis catalyst of formula (4) is represented by the structure of formula (5)

Wherein:

R¹is hydrogen;

R²is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; in general, R²Is unsubstituted phenyl, substituted phenyl, C₁-C₆Alkyl or substituted 1-propenyl; or R¹And R²Linked together to form an optionally substituted indenylene group;

R^bis hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; in general, R^bIs unsubstituted C₁-C₁₀Alkyl, substituted C₁-C₁₀Alkyl, unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl or substituted C₅-C₂₄An aryl group; in general, R^bIs methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R^aAnd R^bLinked together to form a five or six membered heterocyclic ring having a sulfoxide group; in general, R^aAnd R^bLinked together to form tetrahydrothiophene oxide;

X¹and X²Independently halogen, trifluoroacetate, perfluorophenol or nitrate; generally, X¹And X²Independently Cl, Br, I or F; in general, X¹And X²Independently is Cl;

R³is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; in general, R³Is unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl, C substituted by up to three substituents selected from₅-C₂₄Aryl: unsubstituted C₁-C₂₀Alkyl, substituted C₁-C₂₀Alkyl, unsubstituted C₁-C₂₀Heteroalkyl, substituted C₁-C₂₀Heteroalkyl, unsubstitutedC of (A)₅-C₂₄Aryl, substituted C₅-C₂₄Aryl, unsubstituted C₅-C₂₄Heteroaryl, substituted C₅-C₂₄Heteroaryl, unsubstituted C₆-C₂₄Aralkyl, substituted C₆-C₂₄Aralkyl, unsubstituted C₆-C₂₄Alkylaryl, substituted C₆-C₂₄Alkaryl and halide groups; in general, R³Is adamantyl, 2,4, 6-trimethylphenyl, 2, 6-diisopropylphenyl, 2-isopropyl-6-methylphenyl, 2-isopropyl-phenyl or 2-methyl-phenyl; and is

R⁴Is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; in general, R⁴Is unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl or C substituted by up to three substituents selected from₅-C₂₄Aryl: unsubstituted C₁-C₂₀Alkyl, substituted C₁-C₂₀Alkyl, unsubstituted C₁-C₂₀Heteroalkyl, substituted C₁-C₂₀Heteroalkyl, unsubstituted C₅-C₂₄Aryl, substituted C₅-C₂₄Aryl, unsubstituted C₅-C₂₄Heteroaryl, substituted C₅-C₂₄Heteroaryl, unsubstituted C₆-C₂₄Aralkyl, substituted C₆-C₂₄Aralkyl, unsubstituted C₆-C₂₄Alkylaryl, substituted C₆-C₂₄Alkaryl and halide groups; in general, R⁴Is 2,4, 6-trimethylphenyl, 2-isopropyl-phenyl, 2, 6-diisopropylphenyl, 2-isopropyl-6-methylphenyl or 2-methyl-phenyl.

Non-limiting examples of olefin metathesis catalysts represented by the structure of formula (5) are described in Table (1), where X¹Is Cl, and X²Is Cl.

Table (1): an olefin metathesis catalyst of formula (5)

Wherein: mes isMipp is

DIPP isAdamantyl isIPP is2-Me-C₆H₅Is composed ofMe is CH₃-, n-Bu is [ CH₃-(CH₂)₃-]Ph is

And isIs [ - (CH)₂)₄-]。

When Q is of the structure- [ CR ]¹¹＝CR¹³]A diatomic bond of (A) and R¹¹And R¹³When M is ruthenium and hydrogen, the olefin metathesis catalyst of formula (4) is represented by the structure of formula (6)

Wherein:

R¹is hydrogen;

R²is unsubstituted phenyl, substituted phenyl, C₁-C₆Alkyl or substituted 1-propenyl; or R¹And R²Linked together to form an optionally substituted indenylene group;

R^ais hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; r^aIs unsubstituted C₁-C₁₀Alkyl, substituted C₁-C₁₀Alkyl, unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl or substituted C₅-C₂₄An aryl group;

R^bis hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; r^bIs unsubstituted C₁-C₁₀Alkyl, substituted C₁-C₁₀Alkyl, unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl or substituted C₅-C₂₄An aryl group; or R^aAnd R^bLinked together to form a five or six membered heterocyclic ring having a sulfoxide group;

X¹and X²Independently halogen, trifluoroacetate, perfluorophenol or nitrate; x¹And X²Independently Cl, Br, I or F; in general, X¹And X²Independently is Cl;

R³is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; in general, R³Is unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl, C substituted by up to three substituents selected from₅-C₂₄Aryl: unsubstituted C₁-C₂₀Alkyl, substituted C₁-C₂₀Alkyl, unsubstituted C₁-C₂₀Heteroalkyl, substituted C₁-C₂₀Heteroalkyl, unsubstituted C₅-C₂₄Aryl, substituted C₅-C₂₄Aryl, unsubstituted C₅-C₂₄Heteroaryl, substituted C₅-C₂₄Heteroaryl, unsubstituted C₆-C₂₄Aralkyl, substituted C₆-C₂₄Aralkyl, unsubstituted C₆-C₂₄Alkylaryl, substituted C₆-C₂₄Alkaryl and halide groups; in general, R³Is adamantyl, 2,4, 6-trimethylphenyl, 2, 6-diisopropylphenyl, 2-isopropyl-6-methylphenyl, 2-isopropyl-phenyl or 2-methyl-phenyl; and is

R⁴Is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; in general, R⁴Is unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl or C substituted by up to three substituents selected from₅-C₂₄Aryl: unsubstituted C₁-C₂₀Alkyl, substituted C₁-C₂₀Alkyl, unsubstituted C₁-C₂₀Heteroalkyl, substituted C₁-C₂₀Heteroalkyl, unsubstituted C₅-C₂₄Aryl, substituted C₅-C₂₄Aryl, unsubstituted C₅-C₂₄Heteroaryl, substituted C₅-C₂₄Heteroaryl, unsubstituted C₆-C₂₄Aralkyl, substituted C₆-C₂₄Aralkyl, unsubstituted C₆-C₂₄Alkylaryl, substituted C₆-C₂₄Alkaryl and halide groups; in general, R⁴Is 2,4, 6-trimethylphenyl, 2-isopropyl-phenyl, 2, 6-diisopropylphenyl, 2-isopropyl-6-methylphenyl or 2-methyl-phenyl.

Non-limiting examples of olefin metathesis catalysts represented by the structure of formula (6) are described in table (2), where X¹Is Cl, and X²Is Cl.

Table (2): an olefin metathesis catalyst of formula (6)

When Y is N, X⁵Is CR^3AAnd M is ruthenium, the olefin metathesis catalyst of formula (4) is represented by the structure of formula (7)

Wherein:

R¹is hydrogen;

R^bis hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; in general, R^bIs unsubstituted C₁-C₁₀Alkyl, substituted C₁-C₁₀Alkyl, unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl or substituted C₅-C₂₄An aryl group; in general, R^bIs methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R^aAnd R^bLinked together to form a five or six membered heterocyclic ring having a sulfoxide group;

X¹and X²Independently halogen, trifluoroacetate, perfluorophenol or nitrate; generally, X¹And X²Independently Cl, Br, I or F; in general, X¹And X²Independently is Cl;

R³is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl orSubstituted heteroatom-containing hydrocarbyl; in general, R³Is unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl, C substituted by up to three substituents selected from₅-C₂₄Aryl: unsubstituted C₁-C₂₀Alkyl, substituted C₁-C₂₀Alkyl, unsubstituted C₁-C₂₀Heteroalkyl, substituted C₁-C₂₀Heteroalkyl, unsubstituted C₅-C₂₄Aryl, substituted C₅-C₂₄Aryl, unsubstituted C₅-C₂₄Heteroaryl, substituted C₅-C₂₄Heteroaryl, unsubstituted C₆-C₂₄Aralkyl, substituted C₆-C₂₄Aralkyl, unsubstituted C₆-C₂₄Alkylaryl, substituted C₆-C₂₄Alkaryl and halide groups; in general, R³Is adamantyl, 2,4, 6-trimethylphenyl, 2, 6-di-isopropylphenyl, 2-methyl-6-tert-butylphenyl, 2-isopropyl-6-methylphenyl, 2-isopropyl-phenyl, 2, 6-diethylphenyl, 2-ethyl-6-methylphenyl or 2-methyl-phenyl;

R¹¹、R¹²、R¹³and R¹⁴Independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; in general, R¹¹、R¹²、R¹³And R¹⁴Independently hydrogen, unsubstituted C₁-C₁₂Alkyl, substituted C₁-C₁₂Alkyl, unsubstituted C₄-C₁₂Cycloalkyl, substituted C₄-C₁₂Cycloalkyl, unsubstituted C₅-C₂₄Aryl, substituted C₅-C₂₄Aryl, unsubstituted C₅-C₂₄Heteroaryl, substituted C₅-C₂₄Heteroaryl, unsubstituted C₆-C₂₄Aralkyl, substituted C₆-C₂₄Aralkyl, unsubstituted C₆-C₂₄Heteroaralkyl or substituted C₆-C₂₄Heteroaromatic compoundsAn alkyl group; in general, R¹¹And R¹²Independently is methyl, and R¹³And R¹⁴Independently is hydrogen;

R^3Ais hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; in general, R^3AIs unsubstituted C₁-C₁₂Alkyl, substituted C₁-C₁₂Alkyl, unsubstituted C₄-C₁₂Cycloalkyl, substituted C₄-C₁₂Cycloalkyl, unsubstituted C₅-C₂₄Aryl, substituted C₅-C₂₄Aryl, unsubstituted C₅-C₂₄Heteroaryl, substituted C₅-C₂₄Heteroaryl, unsubstituted C₆-C₂₄Aralkyl, substituted C₆-C₂₄Aralkyl, unsubstituted C₆-C₂₄Heteroaralkyl or substituted C₆-C₂₄A heteroaralkyl group; in general, R^3AIs methyl, ethyl, n-propyl or phenyl; or R^3ATogether with R⁴May form, together with the carbon atom to which they are attached, a five-to ten-membered cycloalkyl or heterocyclic ring; and

R⁴is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; in general, R⁴Is unsubstituted C₁-C₁₂Alkyl, substituted C₁-C₁₂Alkyl, unsubstituted C₄-C₁₂Cycloalkyl, substituted C₄-C₁₂Cycloalkyl, unsubstituted C₅-C₂₄Aryl, substituted C₅-C₂₄Aryl, unsubstituted C₅-C₂₄Heteroaryl, substituted C₅-C₂₄Heteroaryl, unsubstituted C₆-C₂₄Aralkyl, substituted C₆-C₂₄Aralkyl, unsubstituted C₆-C₂₄Heteroaralkyl or substituted C₆-C₂₄A heteroaralkyl group; in general, R⁴Is methyl, ethyl, n-propyl or phenyl.

Olefin metathesis catalysis represented by the structure of formula (7)Non-limiting examples of agents are described in Table (3), where X¹Is Cl, X²Is Cl, R¹¹Is methyl, R¹²Is methyl, R¹³Is hydrogen, and R¹⁴Is hydrogen.

Table (3): an olefin metathesis catalyst of formula (7)

Wherein EMP is

When L is¹A CAAC ligand of the formula:

m is 0 and M is ruthenium, the olefin metathesis catalyst of formula (1) is represented by the structure of formula (7A)

Wherein X¹、X²、R¹、R²、R^aAnd R^bAs defined herein;

x is-CR^1aR^2a-；

a is 1 or 2;

R^1ais H, optionally substituted C_1-24Alkyl, optionally substituted C_3-10Cycloalkyl, halogen, optionally substituted C₅-C₂₄Aryl, optionally substituted C₆-C₂₄Aralkyl, optionally substituted C₁-C₂₀Heteroalkyl, -C (O) R²¹、-OR²²、CN、-NR²³R²⁴、NO₂、-CF₃、-S(O)_xR²⁵、-P(O)(OH)₂、-OP(O)(OH)₂、-SR²⁷Or together with R^2aForm, together with the carbon atom to which they are attached, an optionally substituted spiromonocyclic or spiropolycyclic C_3-10Cycloalkyl or spiroheterocycle, or together with R³Or together with R⁴Forming an optionally substituted polycyclic ring;

R^2ais H, optionally substituted C_1-24Alkyl, optionally substituted C_3-10Cycloalkyl, halogen, optionally substituted C₅-C₂₄Aryl, optionally substituted C₆-C₂₄Aralkyl, optionally substituted C₁-C₂₀Heteroalkyl, -C (O) R²¹、-OR²²、CN、-NR²³R²⁴、NO₂、-CF₃、-S(O)_xR²⁵、-P(O)(OH)₂、-OP(O)(OH)₂、-SR²⁷Or together with R^1aForm a spiro monocyclic or spiro polycyclic C with the carbon atom to which they are attached_3-10Cycloalkyl or spiroheterocycle, or together with R³Or together with R⁴Forming an optionally substituted polycyclic ring;

y is-CR^1bR^2b-；

b is 0, 1 or 2;

R^1bis H, optionally substituted C_1-24Alkyl, optionally substituted C_3-10Cycloalkyl, halogen, optionally substituted C₅-C₂₄Aryl, optionally substituted C₆-C₂₄Aralkyl, optionally substituted C₁-C₂₀Heteroalkyl, -C (O) R²¹、-OR²²、CN、-NR²³R²⁴、NO₂、-CF₃、-S(O)_xR²⁵、-P(O)(OH)₂、-OP(O)(OH)₂、-SR²⁷Or together with R^2bForm a five-, six-or ten-membered cycloalkyl or heterocycle with the carbon atom to which they are attached;

R^2bis H, optionally substituted C_1-24Alkyl, optionally substituted C_3-10Cycloalkyl, halogen, optionally substituted C₅-C₂₄Aryl, optionally substituted C₆-C₂₄Aralkyl, optionally substituted C₁-C₂₀Heteroalkyl, -C (O) R²¹、-OR²²、CN、-NR²³R²⁴、NO₂、-CF₃、-S(O)_xR²⁵、-P(O)(OH)₂、-OP(O)(OH)₂、-SR²⁷Or together with R^1bForm a five-, six-or ten-membered cycloalkyl or heterocycle with the carbon atom to which they are attached;

R^3ais H, optionally substituted C_1-24Alkyl, halogen, -C (O) R²¹、-OR²²、CN、-NR²³R²⁴、NO₂、-CF₃、-S(O)_xR²⁵、-P(O)(OH)₂、-OP(O)(OH)₂、-SR²⁷Optionally substituted heterocycle, optionally substituted C_3-10Cycloalkyl, optionally substituted C_5-24Aryl, optionally substituted C_3-8Cycloalkenyl, or together with R^1aOr together with R^2aOptionally substituted polycyclic rings may be formed, or together with R^3aOptionally substituted spiromonocyclic or spiropolycyclic C may be formed_3-10A cycloalkyl group;

R^3bis H, optionally substituted C_1-24Alkyl, halogen, -C (O) R²¹、-OR²²、CN、-NR²³R²⁴、NO₂、-CF₃、-S(O)_xR²⁵、-P(O)(OH)₂、-OP(O)(OH)₂、-SR²⁷Optionally substituted heterocycle, optionally substituted C_3-10Cycloalkyl, optionally substituted C_5-24Aryl, optionally substituted C_3-8Cycloalkenyl, or together with R^1aOr together with R^2aOptionally substituted polycyclic rings may be formed, or together with R³Optionally substituted spiromonocyclic or spiropolycyclic C may be formed_3-10A cycloalkyl group;

R^4ais H, optionally substituted C_1-24Alkyl, halogen, -C (O) R²¹、-OR²²、CN、-NR²³R²⁴、NO₂、-CF₃、-S(O)_xR²⁵、-P(O)(OH)₂、-OP(O)(OH)₂、-SR²⁷Optionally substituted heterocycle, optionally substituted C_3-10Cycloalkyl, optionally substituted C_5-24Aryl, optionally substituted C_3-8Cycloalkenyl, or together with R^1aOr together with R^2aOptionally substituted polycyclic rings may be formed, or together with R^4aOptionally substituted spiromonocyclic or spiropolycyclic C may be formed_3-10A cycloalkyl group;

R^4bis H, optionally substituted C_1-24Alkyl, halogen, -C (O) R²¹、-OR²²、CN、-NR²³R²⁴、NO₂、-CF₃、-S(O)_xR²⁵、-P(O)(OH)₂、-OP(O)(OH)₂、-SR²⁷Optionally substituted heterocycle, optionally substituted C_3-10Cycloalkyl, optionally substituted C_5-24Aryl, optionally substituted C_3-8Cycloalkenyl, or together with R^1aOr together with R^2aOptionally substituted polycyclic rings may be formed, or together with R⁴Optionally substituted spiromonocyclic or spiropolycyclic C may be formed_3-10A cycloalkyl group;

R⁵is H, optionally substituted C_1-24Alkyl, halogen, -C (O) R²¹、-OR²²、CN、-NR²³R²⁴、NO₂、-CF₃、-S(O)_xR²⁵、-P(O)(OH)₂、-OP(O)(OH)₂、-SR²⁷Optionally substituted heterocycle, optionally substituted C_3-10Cycloalkyl, optionally substituted C_5-24Aryl, optionally substitutedC of (A)_3-8Cycloalkenyl, or together with R⁶Optionally substituted polycyclic rings may be formed;

R⁶is H, optionally substituted C_1-24Alkyl, halogen, -C (O) R²¹、-OR²²、CN、-NR²³R²⁴、NO₂、-CF₃、-S(O)_xR²⁵、-P(O)(OH)₂、-OP(O)(OH)₂、-SR²⁷Optionally substituted heterocycle, optionally substituted C_3-10Cycloalkyl, optionally substituted C_5-24Aryl, optionally substituted C_3-8Cycloalkenyl, or together with R⁵Or together with R⁷Optionally substituted polycyclic rings may be formed;

R⁷is H, optionally substituted C_1-24Alkyl, halogen, -C (O) R²¹、-OR²²、CN、-NR²³R²⁴、NO₂、-CF₃、-S(O)_xR²⁵、-P(O)(OH)₂、-OP(O)(OH)₂、-SR²⁷Optionally substituted heterocycle, optionally substituted C_3-10Cycloalkyl, optionally substituted C_5-24Aryl, optionally substituted C_3-8Cycloalkenyl, or together with R⁶Or together with R⁸Optionally substituted polycyclic rings may be formed;

R⁸is H, optionally substituted C_1-24Alkyl, halogen, -C (O) R²¹、-OR²²、CN、-NR²³R²⁴、NO₂、-CF₃、-S(O)_xR²⁵、-P(O)(OH)₂、-OP(O)(OH)₂、-SR²⁷Optionally substituted heterocycle, optionally substituted C_3-10Cycloalkyl, optionally substituted C_5-24Aryl, optionally substituted C_3-8Cycloalkenyl, or together with R⁷Or together with R⁹Optionally substituted polycyclic rings may be formed;

R⁹is H, optionally substituted C_1-24Alkyl, halogen, -C (O) R²¹、-OR²²、CN、-NR²³R²⁴、NO₂、-CF₃、-S(O)_xR²⁵、-P(O)(OH)₂、-OP(O)(OH)₂、-SR²⁷Optionally substituted heterocycle, optionally substituted C_3-10Cycloalkyl, optionally substituted C_5-24Aryl, optionally substituted C_3-8Cycloalkenyl, or together with R⁸Can form multiple rings;

R²¹is OH, OR²⁶、NR²³R²⁴Optionally substituted C_1-24Alkyl, optionally substituted C_3-10Cycloalkyl, optionally substituted heterocycle, optionally substituted C_5-24Aryl or optionally substituted C_3-8A cycloalkenyl group;

R²²is H, optionally substituted C_1-24Alkyl, optionally substituted C_3-10Cycloalkyl, optionally substituted heterocycle, optionally substituted C_5-24Aryl or optionally substituted C_3-8A cycloalkenyl group;

R²³is H, optionally substituted C_1-24Alkyl, optionally substituted C_3-10Cycloalkyl, optionally substituted heterocycle, optionally substituted C_5-24Aryl or optionally substituted C_3-8A cycloalkenyl group;

R²⁴is H, optionally substituted C_1-24Alkyl, optionally substituted C_3-10Cycloalkyl, optionally substituted heterocycle, optionally substituted C_5-24Aryl or optionally substituted C_3-8A cycloalkenyl group;

R²⁵is H, optionally substituted C_1-24Alkyl, OR²²、-NR²³R²⁴Optionally substituted heterocycle, optionally substituted C_3-10Cycloalkyl, optionally substituted C_5-24Aryl or optionally substituted C_3-8A cycloalkenyl group;

R²⁶is optionally substituted C_1-24Alkyl, optionally substituted C_3-10Cycloalkyl, optionally substituted heterocycle, optionally substituted C_5-24Aryl or optionally substituted C_3-8A cycloalkenyl group;

R²⁷is H, optionally substituted C_1-24Alkyl, optionallySubstituted C_3-10Cycloalkyl, optionally substituted heterocycle, optionally substituted C_5-24Aryl or optionally substituted C_3-8A cycloalkenyl group;

x is 1 or 2; and with the proviso that

a. When a is 2, the "X-X" bond may be saturated or unsaturated;

b. when b is 2, the "Y-Y" bond may be saturated or unsaturated;

c. when a is 2 and the "X-X" bond is unsaturated, R^2aIs absent;

d. when b is 1, R^3aAnd R^4aAre not present;

e. when b is 2, R^3aAnd R^4aAre not present; and

f. when b is 2 and the "Y-Y" bond is unsaturated, R^2bIs absent.

CAAC ligands according to the values of a, b, X and YThe moiety (A) of (A) is represented by a structure selected from Table (4).

Table (4): structure of part (A) of CAAC ligand

Wherein: r¹、R²、R^a、R^b、R^3a、R^3b、R^4a、R^4b、R⁵、R⁶、R⁷、R⁸、R⁹、R^1a、R^1b、X¹、X²X and Y are as defined herein.

The nomenclature of the structure of formula (7A) is determined by the part (a) structure selected from table (4). For example, due to the presence of the moiety (a2) in the CAAC ligand, the following structure is designated formula (7a 2).

Table (5): an olefin metathesis catalyst of formula (7A)

Wherein: r¹、R²、R^a、R^b、R^3a、R^3b、R^4a、R^4b、R⁵、R⁶、R⁷、R⁸、R⁹、R^1a、R^1b、X¹、X²X and Y are as defined herein.

When L is¹Is composed ofAn N-heterocyclic carbene ligand of the formula, and

is composed of

And X³And X⁴Independently S, and M is ruthenium, the olefin metathesis catalyst of formula (2) is represented by the structure of formula (8)

Wherein:

R^ais unsubstituted C₁-C₁₀Alkyl, substituted C₁-C₁₀Alkyl, unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl or substituted C₅-C₂₄An aryl group; in general, R^aIs methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl orA phenyl group;

R^bis unsubstituted C₁-C₁₀Alkyl, substituted C₁-C₁₀Alkyl, unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl or substituted C₅-C₂₄An aryl group; in general, R^bIs methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or phenyl; or R^aAnd R^bLinked together to form a five or six membered heterocyclic ring having a sulfoxide group;

R³is unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl, C substituted by up to three substituents selected from₅-C₂₄Aryl: unsubstituted C₁-C₂₀Alkyl, substituted C₁-C₂₀Alkyl, unsubstituted C₁-C₂₀Heteroalkyl, substituted C₁-C₂₀Heteroalkyl, unsubstituted C₅-C₂₄Aryl, substituted C₅-C₂₄Aryl, unsubstituted C₅-C₂₄Heteroaryl, substituted C₅-C₂₄Heteroaryl, unsubstituted C₆-C₂₄Aralkyl, substituted C₆-C₂₄Aralkyl, unsubstituted C₆-C₂₄Alkylaryl, substituted C₆-C₂₄Alkaryl and halide groups; in general, R³Is adamantyl, 2,4, 6-trimethylphenyl, 2, 6-diisopropylphenyl, 2-methyl-6-tert-butylphenyl, 2-isopropyl-6-methylphenyl, 2-isopropyl-phenyl, 2, 6-diethylphenyl, 2-ethyl-6-methylphenyl, 2,4, 6-trifluorophenyl, 2, 6-difluorophenyl, 3, 5-di-tert-butylphenyl, 2, 4-dimethylphenyl or 2-methyl-phenyl;

R⁴is unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl, C substituted by up to three substituents selected from₅-C₂₄Aryl: unsubstituted C₁-C₂₀Alkyl, substituted C₁-C₂₀Alkyl, unsubstituted C₁-C₂₀Heteroalkyl, substituted C₁-C₂₀Heteroalkyl, unsubstituted C₅-C₂₄Aryl, substituted C₅-C₂₄Aryl, unsubstituted C₅-C₂₄Heteroaryl, substituted C₅-C₂₄Heteroaryl, unsubstituted C₆-C₂₄Aralkyl, substituted C₆-C₂₄Aralkyl, unsubstituted C₆-C₂₄Alkylaryl, substituted C₆-C₂₄Alkaryl and halide groups; in general, R⁴Is 2,4, 6-trimethylphenyl, 2, 6-diisopropylphenyl, 2-methyl-6-tert-butylphenyl, 2-isopropyl-6-methylphenyl, 2-isopropyl-phenyl, 2, 6-diethylphenyl, 2-ethyl-6-methylphenyl, 2,4, 6-trifluorophenyl, 2, 6-difluorophenyl, 3, 5-di-tert-butylphenyl, 2, 4-dimethylphenyl or 2-methyl-phenyl;

R¹is hydrogen, and R²Is unsubstituted phenyl, substituted phenyl, C₁-C₆Alkyl or substituted 1-propenyl; or R¹And R²Linked together to form an optionally substituted indenylene group;

R¹¹、R¹²、R¹³and R¹⁴Independently is C₁-C₆Alkyl or hydrogen; in general, R¹¹Is hydrogen or methyl, R¹²Is hydrogen or methyl, R¹³Is hydrogen, and R¹⁴Is hydrogen; in general, R¹¹、R¹²、R¹³And R¹⁴Independently is hydrogen; and

R^x、R^y、R^wand R^zIndependently is C₁-C₆Alkyl, hydrogen, halogen, unsubstituted phenyl or substituted phenyl; in general, R^xIs methyl, hydrogen or Cl, R^yIs hydrogen, R^wIs hydrogen, R^zIs Cl, tert-butyl, hydrogen or phenyl; or R^xAnd R^yLinked together to form an unsubstituted bicyclic or polycyclic aryl group or a substituted bicyclic or polycyclic aryl group(ii) a Or R^wAnd R^zLinked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^yAnd R^wLinked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl.

Non-limiting examples of olefin metathesis catalysts represented by the structure of formula (8) are described in Table (6), where R^aIs methyl, R^bIs methyl, R¹¹Is hydrogen, R¹²Is hydrogen, R¹³Is hydrogen, R¹⁴Is hydrogen, R^yIs hydrogen, and R^wIs hydrogen.

Table (6): an olefin metathesis catalyst of formula (8)

Non-limiting examples of catalysts useful in the present invention are represented by the following structures:

when L is¹Is a CAAC ligand, andis composed ofAnd X³And X⁴Independently S, and M is ruthenium, the olefin metathesis catalyst of formula (2) is represented by the structure of formula (8A)

Wherein: r¹、R²、R^a、R^b、R^3a、R^3b、R^4a、R^4b、R⁵、R⁶、R⁷、R⁸、R⁹、R^x、R^y、R^z、R^wX, Y, a and b are as defined herein.

The nomenclature of the structure of formula (8A) is determined by the part (a) structure selected from table (4). For example, due to the presence of the moiety (a10) in the CAAC ligand, the following structure is designated formula (8a 10).

Watch (8A10)

Table (7): an olefin metathesis catalyst of formula (8A)

Wherein: r¹、R^1a、R^1b、R²、R^a、R^b、R^3a、R^3b、R^4a、R^4b、R⁵、R⁶、R⁷、R⁸、R⁹、R^x、R^y、R^z、R^wX, Y, a and b are as defined herein.

In other embodiments of the invention, the group 8 metal olefin metathesis catalysts of the invention are represented by the general structure of formula (9)

Wherein: m is a group 8 transition metal; typically, M is ruthenium or osmium; typically, M is ruthenium;

L¹and L²Independently a neutral electron donor ligand;

n is 0 or 1; typically, n is 0;

m is 0, 1 or 2; typically, m is 0 or 1; typically, m is 0;

R^aais unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; in general, R^aaIs unsubstituted C₁-C₁₀Alkyl, substituted C₁-C₁₀Alkyl, unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl or substituted C₅-C₂₄An aryl group; in general, R^aaIs methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl, benzyl or phenyl;

R^bbis unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; in general, R^bbIs unsubstituted C₁-C₁₀Alkyl, substituted C₁-C₁₀Alkyl, unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl or substituted C₅-C₂₄An aryl group; in general, R^bbIs methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl, benzyl or phenyl;

R^aaand R^bbCan be connected with themThe connected nitrogen atoms are connected to form a five-, six-or seven-membered heterocyclic ring;

R^ccis unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; in general, R^ccIs unsubstituted C₁-C₁₀Alkyl, substituted C₁-C₁₀Alkyl, unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl or substituted C₅-C₂₄An aryl group; in general, R^ccIs methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl, benzyl or phenyl;

R^ddis unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl; in general, R^dIs unsubstituted C₁-C₁₀Alkyl, substituted C₁-C₁₀Alkyl, unsubstituted C₃-C₁₀Cycloalkyl, substituted C₃-C₁₀Cycloalkyl, unsubstituted C₅-C₂₄Aryl or substituted C₅-C₂₄An aryl group; in general, R^ddIs methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl, benzyl or phenyl;

R^ccand R^ddMay be linked to the nitrogen atom to which they are linked to form a five-, six-or seven-membered heterocyclic ring;

R^bband R^ccMay be linked to the nitrogen atom to which they are attached to form a five-, six-or seven-membered heterocyclic ring;

X¹and X²Independently, an anionic ligand; generally, X¹And X²Independently halogen, trifluoroacetate, perfluorophenol or nitrate; in general, X¹And X²Independently chlorine, bromine, iodine or fluorine;

In some embodiments of formula (9),

byRepresents; wherein: m, X¹、X²、X³、X⁴、R^x、R^y、R^wAnd R^zAs defined herein.

In some embodiments of formula (9), L¹Is composed of

Of the representation

Or L¹Is composed ofA CAAC ligand represented; wherein Q¹、Q²、p、q、R^3a、R^3b、R^4a、R^4b、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、X⁵、Y⁵A and b are as defined herein.

When M is Ru, n is 0, M is 0 and L¹Is a structure

The present invention provides a ligand of the formulaA catalyst represented by the formula (I) andbyWhen shown, the invention provides a structureCatalysts of the formulae

Wherein R is¹、R²、R³、R⁴、R^aa、R^bb、R^cc、R^dd、X¹、X²、X³、X⁴、R¹¹、R¹²、R¹³、R¹⁴、R^x、R^y、R^wAnd R^zAs defined herein.

When M is Ru, n is 0, M is 0 and L¹In the case of CAAC ligands, the present invention provides catalysts represented by the structure of formula (10A)

Wherein: r¹、R²、X¹、X²、R^3a、R^3b、R^4a、R^4b、R^aa、R^bb、R^cc、R^dd、R⁵、R⁶、R⁷、R⁸、R⁹X, Y, a and b are as defined herein.

The nomenclature of the structure of formula (10A) is determined by the part (A) structure selected from Table (4). For example, due to the presence of the moiety (a10) in the CAAC ligand, the following structure is designated formula (10a 10).

Table (8): an ene of the formula (10A)Hydrocarbon metathesis catalysts

Wherein: r¹、R^1a、R^1b、R²、R^a、R^b、R^3a、R^3b、R^4a、R^4b、R^aa、R^bb、R^cc、R^dd、R⁵、R⁶、R⁷、R⁸、R⁹、R^x、R^y、R^z、R^wX, Y, a and b are as defined herein.

When M is Ru, n is 0, M is 0,

Is represented by X³And X⁴Is S, and L¹When a ligand, the present invention provides a catalyst represented by the structure of formula (12A)

Wherein: r¹、R²、R^3a、R^3b、R^4a、R^4b、R^aa、R^bb、R^cc、R^dd、R⁵、R⁶、R⁷、R⁸、R⁹、R^x、R^y、R^w、R^zX, Y, a and b are as defined herein.

The nomenclature of the structure of formula (12A) is determined by the part (A) structure selected from Table (4). For example, due to the presence of the moiety (a5) in the CAAC ligand, the following structure is designated formula (12a 5).

Table (9): an olefin metathesis catalyst of formula (12A)

Wherein: r¹、R²、R^1a、R^1b、R^3a、R^3b、R^4a、R^4b、R^aa、R^bb、R^cc、R^dd、R⁵、R⁶、R⁷、R⁸、R⁹、R^x、R^y、R^w、R^zX, Y, a and b are as defined herein.

Non-limiting examples of catalysts useful in the present invention are represented by the following structures:

description of embodiments of macromolecular Compounds

In one embodiment, the ring-closing metathesis macrocycle product comprises a product internal olefin, wherein the product internal olefin is in the Z-configuration.

In some embodiments, the present invention provides methods of making compounds (i.e., products, olefin products; e.g., ring-closing metathesis products) having carbon-carbon double bonds (e.g., product internal olefins) with a Z: E ratio greater than 95:5, greater than 96:4, greater than 97:3, greater than 98:2, or in some cases greater than 99: 1. In some cases, about 100% of the carbon-carbon double bonds produced in the metathesis reaction may have the Z configuration. Z or cis selectivity may also be expressed as a percentage of the product formed (e.g., ring-closing metathesis product). In some cases, the product (e.g., ring-closing metathesis product) may be greater than 50% Z, greater than 60% Z, greater than 70% Z, greater than 80% Z, greater than 90% Z, greater than 95% Z, greater than 96% Z, greater than 97% Z, greater than about 98% Z, greater than 99% Z, or, in some cases, greater than 99.5% Z.

In one embodiment, the ring-closing metathesis reaction product has a carbon-carbon double bond of Z configuration and is represented by the structure of formula (a):

wherein:

q is 1,2, 3, or 4; and

p is 4,5, 6 or 7.

In another embodiment, at least one ring-closing metathesis product is represented by the structure of formula (a), where q is 2 and p is 4 or 6.

In another embodiment, at least one ring-closing metathesis product is represented by the structure of formula (a), where q is 1,2, 3, or 4, and p is 6 or 7.

In another embodiment, at least one ring-closing metathesis product is represented by the structure of formula (a), where q is 1 or 2, and p is 6.

In another embodiment, at least one ring-closing metathesis product is represented by the structure of formula (a), where q is 1,2, 3, or 4, and p is 7.

In another embodiment, at least one ring-closing metathesis product is represented by the structure of formula (a), where q is 1 and p is 6.

In another embodiment, the ring-closing metathesis reaction product has a carbon-carbon double bond of the Z configuration and is represented by the structure of formula (B):

wherein:

r is 1,2, 3 or 4; and

v is 4,5, 6 or 7.

In another embodiment, at least one ring-closing metathesis product is represented by the structure of formula (B), where r is 2 and v is 4 or 6.

In another embodiment, at least one ring-closing metathesis product is represented by the structure of formula (B), where r is 1,2, 3, or 4, and v is 6 or 7.

In another embodiment, at least one ring-closing metathesis product is represented by the structure of formula (B), where r is 1 or 2, and v is 6.

In another embodiment, at least one ring-closing metathesis product is represented by the structure of formula (B), where r is 1,2, 3, or 4, and v is 7.

In another embodiment, at least one ring-closing metathesis product is represented by the structure of formula (B), where r is 1 and v is 6.

In one embodiment, the diene feedstock bearing Z-olefin moieties may be represented by formula (E):

wherein:

R^eis H, methyl, ethyl or propyl;

q is 1,2, 3, or 4;

p is 4,5, 6 or 7.

In one embodiment, the diene feedstock bearing Z-olefin moieties may be represented by formula (E), wherein R^eIs methyl, q is 2, and p is 4 or 6.

In one embodiment, the diene feedstock bearing Z-olefin moieties may be represented by formula (E), wherein R^eIs ethyl, q is 1,2, 3 or 4, and p is 6 or 7.

At one endIn one embodiment, the diene feedstock bearing Z-olefin moieties may be represented by formula (E), wherein R^eIs ethyl, q is 1 or 2, and p is 6.

In one embodiment, the diene feedstock bearing Z-olefin moieties may be represented by formula (E), wherein R^eIs ethyl, q is 1,2, 3 or 4, and p is 7.

In one embodiment, the diene feedstock bearing Z-olefin moieties may be represented by formula (E), wherein R^eIs ethyl, q is 1, and p is 6.

In another embodiment, the present invention relates to a process for performing a ring-closing metathesis reaction, comprising: contacting a diene feedstock bearing a Z-alkene moiety of formula (E) with at least one olefin metathesis catalyst of formula (5) under conditions effective to promote the formation of at least one Z-macrocyclic product of formula (a) having a Z-configuration greater than 80% Z.

In another embodiment, the present invention relates to a process for performing a ring-closing metathesis reaction, comprising: contacting a diene feedstock bearing Z-olefinic moieties of formula (E) with at least one olefin metathesis catalyst of formula (6) under conditions effective to promote the formation of at least one Z-macrocyclic product of formula (a) having a Z-configuration greater than 80% Z.

In another embodiment, the present invention relates to a process for performing a ring-closing metathesis reaction, comprising: contacting a diene feedstock bearing Z-olefinic moieties of formula (E) with at least one olefin metathesis catalyst of formula (7) under conditions effective to promote the formation of at least one Z-macrocyclic product of formula (a) having a Z-configuration greater than 80% Z.

In another embodiment, the present invention relates to a process for performing a ring-closing metathesis reaction, comprising: contacting a diene feedstock bearing a Z-alkene moiety of formula (E) with at least one Z-stereoretentive olefin metathesis catalyst of formula (8) under conditions effective to promote the formation of at least one Z-macrocyclic product of formula (a) having a Z-configuration greater than 80% Z.

In another embodiment, the present invention relates to a process for performing a ring-closing metathesis reaction, comprising: contacting a diene feedstock bearing a Z-alkene moiety of formula (E) with at least one Z-stereoretentive olefin metathesis catalyst of formula (8A) under conditions effective to promote the formation of at least one Z-macrocyclic product of formula (a) having a Z-configuration greater than 80% Z.

In another embodiment, the present invention relates to a process for performing a ring-closing metathesis reaction, comprising: contacting a diene feedstock bearing a Z-alkene moiety of formula (E) with at least one Z-stereoretentive olefin metathesis catalyst of formula (9) under conditions effective to promote the formation of at least one Z-macrocyclic product of formula (a) having a Z-configuration greater than 80% Z.

In another embodiment, the present invention relates to a process for performing a ring-closing metathesis reaction, comprising: contacting a diene feedstock bearing a Z-alkene moiety of formula (E) with at least one Z-stereoretentive olefin metathesis catalyst of formula (10) under conditions effective to promote the formation of at least one Z-macrocyclic product of formula (a) having a Z-configuration greater than 80% Z.

In another embodiment, the present invention relates to a process for performing a ring-closing metathesis reaction, comprising: contacting a diene feedstock bearing a Z-alkene moiety of formula (E) with at least one Z-stereoretentive olefin metathesis catalyst of formula (10A) under conditions effective to promote the formation of at least one Z-macrocyclic product of formula (a) having a Z-configuration greater than 80% Z.

In another embodiment, the present invention relates to a process for performing a ring-closing metathesis reaction, comprising: contacting a diene feedstock bearing a Z-alkene moiety of formula (E) with at least one Z-stereoretentive olefin metathesis catalyst of formula (11) under conditions effective to promote the formation of at least one Z-macrocyclic product of formula (a) having a Z-configuration greater than 80% Z.

In another embodiment, the present invention relates to a process for performing a ring-closing metathesis reaction, comprising: contacting a diene feedstock bearing a Z-alkene moiety of formula (E) with at least one Z-stereoretentive olefin metathesis catalyst of formula (12) under conditions effective to promote the formation of at least one Z-macrocyclic product of formula (a) having a Z-configuration greater than 80% Z.

In another embodiment, the present invention relates to a process for performing a ring-closing metathesis reaction, comprising: contacting a diene feedstock bearing a Z-alkene moiety of formula (E) with at least one Z-stereoretentive olefin metathesis catalyst of formula (12A) under conditions effective to promote the formation of at least one Z-macrocyclic product of formula (a) having a Z-configuration greater than 80% Z.

In one embodiment, the present invention provides a method of synthesizing a musk macrocyclic compound represented by formula (a), the method comprising ring-closing metathesis of a diene of formula (E) in the presence of at least one metathesis catalyst under conditions sufficient to form a metathesis product, wherein the at least one metathesis catalyst is represented by the structure of formula (5), and wherein R is^e、q、p、R¹、R²、R^a、R^b、X¹、X²、R³And R⁴As defined herein.

In one embodiment, the present invention provides a method of synthesizing a musk macrocyclic compound represented by formula (a), the method comprising ring-closing metathesis of a diene of formula (E) in the presence of at least one metathesis catalyst under conditions sufficient to form a metathesis product, wherein the at least one metathesis catalyst is represented by the structure of formula (8), and wherein R is^e、q、p、R¹、R²、R^a、R^b、R¹¹、R¹²、R¹³、R¹⁴、R³、R⁴、R^x、R^y、R^zAnd R^wAs defined herein.

In one embodiment, a Z-olefin moiety represented by formula (E) (wherein R is^eIs a methyl group, q is 2, and p is 4 or 6) in the presence of a catalyst represented by the formula (8) wherein R is¹Is hydrogen, R²Is phenyl, ethyl or together with R¹Can form a phenylindenyl group, R^aIs methyl, R^bIs methyl, R¹¹Is hydrogen, R¹²Is hydrogen, R¹³Is hydrogen, R¹⁴Is hydrogen, R³R is 2,4, 6-trimethylphenyl, 2, 6-diisopropylphenyl, 2-methyl-6-tert-butylphenyl, 2-isopropyl-6-methylphenyl, 2-isopropyl-phenyl, 2, 6-diethylphenyl, 2-ethyl-6-methylphenyl, 2,4, 6-trifluorophenyl, 2, 6-difluorophenyl, 3, 5-di-tert-butylphenyl, 2, 4-dimethylphenyl or 2-methyl-phenyl, R is⁴R is 2,4, 6-trimethylphenyl, 2, 6-diisopropylphenyl, 2-methyl-6-tert-butylphenyl, 2-isopropyl-6-methylphenyl, 2-isopropyl-phenyl, 2, 6-diethylphenyl, 2-ethyl-6-methylphenyl, 2,4, 6-trifluorophenyl, 2, 6-difluorophenyl, 3, 5-di-tert-butylphenyl, 2, 4-dimethylphenyl or 2-methyl-phenyl, R is^xIs Cl, R^yIs hydrogen, R^zIs Cl, and R^wIs hydrogen, to give a musk macrocyclic compound of formula (A) with a Z-configuration of more than 80% Z.

In one embodiment, the present invention provides a method for synthesizing a musk macrocyclic compound of formula (a) including ring-closing metathesis of a diene of formula (E) in the presence of at least one metathesis catalyst under conditions sufficient to form a metathesis product, where R is^eIs H, methyl, ethyl or propyl; q is 1,2, 3, or 4; p is 4,5, 6, or 7; wherein the at least one metathesis catalyst is represented by the structure of formula (5), wherein the catalyst is selected from the group consisting of: c591, C731, C625, C763, C663, C641, C647m, C747, C647, C676, C773, C673, C651 and C831 m.

In one embodiment, the present invention provides a method for synthesizing a musk macrocyclic compound of formula (a) including ring-closing metathesis of a diene of formula (E) in the presence of at least one metathesis catalyst under conditions sufficient to form a metathesis product, where R is^eIs H, methyl, ethyl or propyl; q is 1,2, 3, or 4; p is 4,5, 6, or 7; wherein the at least one metathesis catalyst is represented by the structure of formula (8), wherein the catalyst is selected from the group consisting of: c885ss, C785ss, C738ss, C869ss and C725 ss.

In one embodiment, the present invention provides a method of synthesizing a musk macrocycle of formula (B), the method comprisingRing-closing metathesis of a diene of formula (E) in the presence of at least one metathesis catalyst under conditions sufficient to form a metathesis product, wherein R^eIs H, methyl, ethyl or propyl; r is 1,2, 3 or 4; v is 4,5, 6 or 7; wherein the at least one metathesis catalyst is represented by the structure of formula (12), wherein the catalyst is selected from the group consisting of: c801_TU、C701_TU、C885_TU、C881_TU、C799_TU、C951_TUAnd C799u_TU。

In one embodiment, the present invention provides a method of synthesizing dilactones, such as vinyl tridecanoate (x ═ 9) and vinyl undecanedioate (x ═ 7) used in perfumes, wherein the starting materials are obtainable by a cross metathesis reaction in the presence of at least one metal olefin metathesis catalyst of the present invention. The olefin is further reduced and cyclized using known methods.

In one embodiment, the diene feedstock bearing Z-olefin moieties may be represented by formula (F):

wherein:

R^fis H, methyl, ethyl or propyl;

r is 1,2, 3 or 4;

v is 4,5, 6 or 7.

In one embodiment, the diene feedstock bearing Z-olefin moieties may be represented by the formula (F), wherein R^fIs methyl, r is 2, and v is 4 or 6.

In one embodiment, the diene feedstock bearing Z-olefin moieties may be represented by the formula (F), wherein R^fIs ethyl, r is 1,2, 3 or 4, and v is 6 or 7.

In one embodiment, the diene feedstock bearing Z-olefin moieties may be represented by formula (F), whichIn R^fIs ethyl, r is 1 or 2, and v is 6.

In one embodiment, the diene feedstock bearing Z-olefin moieties may be represented by the formula (F), wherein R^fIs ethyl, r is 1,2, 3 or 4, and v is 7.

In one embodiment, the diene feedstock bearing Z-olefin moieties may be represented by the formula (F), wherein R^fIs ethyl, r is 1, and v is 6.

In one embodiment, the present invention provides a method for synthesizing a musk macrocyclic compound of formula (B) comprising ring-closing metathesis of a diene of formula (F) wherein R is ring-closing metathesis in the presence of at least one metathesis catalyst under conditions sufficient to form a metathesis product^fIs H, methyl, ethyl or propyl; r is 1,2, 3 or 4; v is 4,5, 6 or 7; wherein the at least one metathesis catalyst is represented by the structure of formula (5), wherein the catalyst is selected from the group consisting of: c591, C731, C625, C763, C663, C641, C647m, C747, C647, C676, C773, C673, C651 and C831 m.

In one embodiment, the present invention provides a method for synthesizing a musk macrocyclic compound of formula (B) comprising ring-closing metathesis of a diene of formula (F) wherein R is ring-closing metathesis in the presence of at least one metathesis catalyst under conditions sufficient to form a metathesis product^fIs H, methyl, ethyl or propyl; r is 1,2, 3 or 4; v is 4,5, 6 or 7; wherein the at least one metathesis catalyst is represented by the structure of formula (8), wherein the catalyst is selected from the group consisting of: c885ss, C785ss, C738ss, C869ss and C725 ss.

In one embodiment, the present invention provides a method of synthesizing a musk macrocycle represented by formula (K)

The method comprises the following steps:

a) under conditions sufficient to form a metathesis product represented by the structure of formula (J),

in the presence of at least one olefin metathesis catalyst of formula (4), formula (5), formula (6) or formula (7), an olefin represented by formula (G)

Contacting with at least one metathesis reaction participant represented by formula (H):

wherein R is^1mIs H or methyl; OR (OR)^2mIs a protected hydroxyl group, which may be selected from alkyl ether groups; an ester group; a silyl ether group; or a carbonate group; r^3mC being branched or straight chain₁-C₅An alkyl group; x is 2, 3,4 or 5; and y is 5, 6, 7 or 8.

In one embodiment, the present invention provides a method of synthesizing a musk macrocycle represented by formula (K)

The method comprises the following steps:

a) under conditions sufficient to form a metathesis product represented by the structure of formula (J),

in the presence of at least one olefin metathesis catalyst of formula (8), formula (8A), formula (9), formula (10A), formula (11), formula (12A) or formula (13), an olefin represented by formula (G)

Contacting with at least one metathesis reaction participant represented by formula (H):

In one embodiment of the invention, one or both of the first olefin and the second olefin may be an olefin having a terminal double bond.

In one embodiment of the invention, one of the first olefin or the second olefin may be represented by formula (G), wherein: r^1mIs H or methyl; OR (OR)^2mIs a protected hydroxyl group, which may be selected from alkyl ether groups; an ester group; a silyl ether group; or a carbonate group; and x is 2, 3,4 or 5.

In one embodiment of the invention, one of the first olefin or the second olefin may be represented by formula (H), wherein: r^3mC being branched or straight chain₁-C₅An alkyl group; and y is 5, 6, 7 or 8.

In one embodiment of the present invention, the intermediate formed during the cross-metathesis reaction between the first olefin of formula (G) and the second olefin of formula (H) in the presence of at least one ruthenium olefin metathesis catalyst can be represented by formula (J), wherein: r^1mIs H or methyl; OR (OR)^2mIs a protected hydroxyl group selected from the group consisting of alkyl ether groups, ester groups, silyl ether groups, and carbonate groups; r^3mC being branched or straight chain₁-C₅An alkyl group; x is 2, 3,4 or 5; r^3mC being branched or straight chain₁-C₅An alkyl group; and y is 5, 6, 7 or 8.

TABLE (10) macrocyclic Compounds of the musks

Name (R)	y	x
			E/Z Musk lactones	7	6
7-Musk lactone	5	8
			Cyclopentadecenolide	9	3
9-hexadecene-16-lactide	7	5

The intermediate of formula (J) may be formed in the presence of any one of the ruthenium metathesis catalysts represented by formula (1), formula (2), formula (3), formula (4), formula (5), formula (6), formula (7), formula (8A), formula (9), formula (10A), formula (11), formula (12A), or formula (13). The ruthenium catalyst can be selected from any of the structures defined, represented, or exemplified herein.

Macrocyclic products

Common macrocyclic musk compounds include musk lactones (9-and 7-musk lactones), norvalactone (nirvanolide), cyclopentadecenolide, melodiole musk, musk ketene, cyclohexadecetone (velvione), civetone and cyclohexadecetone (globanone).

For example, the first olefinic compound and the second olefinic compound useful in forming 7-musk lactone may be selected from the group consisting of 10- (tert-butoxy) dec-1-ene and oct-7-enoic acid methyl ester or dec-9-en-1-yl acetate and oct-7-enoic acid methyl ester. The first olefinic compound and the second olefinic compound that can be used to form cyclopentadecenolide can be selected from trimethyl (pent-4-en-1-yloxy) silane and ethyl dodecyl-11-enoate. The first olefinic compound and the second olefinic compound useful in forming norvalactone can be selected from 4-methyl-6- (t-butoxy) hex-1-ene and methyl 9-decenoate, or 4-methyl 1-6- (t-butoxy) hex-1-ene and ethyl 9-decenoate, or 3-methylhex-5-en-1-yl propionate and methyl 9-decenoate.

Thus, the process of the present invention, in which a heterodimer is first formed by metathesis and then ring closure is carried out by a macrocyclization step, represents a simpler and cheaper process than RCM in forming macrocyclic musk compounds which can be industrially expanded in an economical manner.

As mentioned above, a variety of macrocyclic derivatives obtained via the process of the invention are useful in the fragrance and fragrance industry. Macrocyclic derivatives include, for example, the compounds listed in table (11).

TABLE (11) macrocyclic products

Experiment of

General information-material and method

Exemplary embodiments provided in accordance with the presently disclosed subject matter include, but are not limited to, the claims and the following embodiments.

All operations were carried out in the absence of air, filled with N, unless otherwise indicated₂In a vacuum atmosphere glove box. Typically the solvent is purified by passing through a solvent purification column. Commercially available substrates were used as received. All solvents and substrates were sparged with Ar and then introduced into a glove box and filtered on neutral alumina (Brokmann I) prior to use. The olefin metathesis catalysts used in the following examples were synthesized according to the procedures described in international patent applications PCT/US2017/046283 and PCT/US 2018/027098.

Kinetic NMR experiments were performed on a Varian 600MHz spectrometer with an AutoX probe. Spectra were analyzed using mestrenova version 8.1.2.¹H and¹³c NMR characterization data were obtained on a Bruker400 with Prodigy broadband cryoprobe and referenced to residual protic solvent.

All reactions involving the metal complexes were carried out in oven-dried glassware under an argon or nitrogen atmosphere using standard Schlenk techniques. Chemicals and solvents were obtained from Sigma Aldrich (Sigma-Aldrich), Strem, Alfa Aesar (Alfa Aesar), na-neoplastification (Nexeo), brentag (brentag), AG Layne and TCI. Commercially available reagents were used as received unless otherwise indicated. Silica gel was purchased from Fisher (0.040 μm-0.063 μm, EMD micropore).

The following abbreviations are used in the examples:

mL of

L liter

DEG C

CD₂Cl₂Deuterated dichloromethane

CDCl₃Deuterated chloroform

C₆D₆Deuterated benzene

Ar argon gas

HCl hydrochloric acid

KHMDS potassium bis (trimethylsilyl) amide

r.t. room temperature

THF tetrahydrofuran

NaHCO₃Sodium bicarbonate

Et₂O diethyl ether

HCl hydrochloric acid

MgSO₄Magnesium sulfate

DCM dichloromethane

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Reaction of olefin derivatives in the presence of metathesis catalysts

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