阅读说明：本技术 一种由二氧化碳制备ε-,ζ-,η-氰基羧酸的方法 (Method for preparing epsilon-, zeta-, eta-cyano carboxylic acid from carbon dioxide ) 是由 孙松 柏君雪 周聪 李渺 于 2021-08-30 设计创作，主要内容包括：本发明涉及医药、有机化工及精细化工领域,具体涉及一种由二氧化碳制备ε-,ζ-,η-氰基羧酸的方法。以烯烃和环酮肟为原料,铱、4CZIPN或钌为催化剂,在还原剂存在下,二甲亚砜做溶剂,2x3W蓝色LED,室温反应12～24小时,然后加入碘甲烷在50℃油浴锅中再进行合成反应1小时得到产物。反应后的产物经过简单后处理即可以高产率得到一系列ε-,ζ-,η-氰基羧酸化合物。各类取代基的二苯乙烯,以及各类取代基的环酮肟都可作为反应底物,得到相应ε-,ζ-,η-氰基羧酸化合物。(The invention relates to the fields of medicine, organic chemical industry and fine chemical industry, in particular to a method for preparing epsilon-, zeta-, eta-cyano carboxylic acid from carbon dioxide. Olefin and cyclic ketoxime are used as raw materials, iridium, 4CZIPN or ruthenium are used as catalysts, dimethyl sulfoxide is used as a solvent in the presence of a reducing agent, 2x3W blue LED is reacted for 12-24 hours at room temperature, and then methyl iodide is added into an oil bath kettle at 50 ℃ for synthesis reaction for 1 hour to obtain a product. The products after the reaction can be processed simply to obtain a series of epsilon-, zeta-, eta-cyano carboxylic acid compounds with high yield. Stilbene with various substituents and cyclic ketoxime with various substituents can be used as reaction substrates to obtain corresponding epsilon-, zeta-, eta-cyano carboxylic acid compounds.)

1. A process for producing an epsilon-, zeta-, eta-cyano carboxylic acid from carbon dioxide, characterized in that: the method comprises the following steps: olefin and cyclic ketoxime are taken as raw materials, iridium, 4CZIPN or ruthenium are taken as photocatalysts, and dimethyl sulfoxide is taken as a solvent in the presence of a reducing agent; and (3) introducing carbon dioxide gas after all the raw materials participating in the reaction are added, and reacting to obtain a series of cyano carboxylic acid compounds.

2. The process for producing an epsilon-, zeta-, eta-cyano carboxylic acid compound as recited in claim 1, wherein: the reaction conditions are as follows: and (3) reacting the 2x3W blue LED at room temperature for 12-24 hours, and then adding the obtained product into an oil bath kettle containing methyl iodide and the temperature of 50 ℃ for reacting for 1 hour.

3. The process for producing an epsilon-, zeta-, eta-cyano carboxylic acid compound as recited in claim 1, wherein: the molar ratio of the olefin to the cyclic ketoxime is 1: 1.5-2.0, and the pressure of carbon dioxide is 0.1 MPa.

4. The process for producing an epsilon-, zeta-, eta-cyano carboxylic acid compound as recited in claim 1, wherein: the olefin has the following structural formula:

r' on the olefin is phenyl, methyl, naphthyl, thienyl or hydrogen; when R' and R are phenyl, the substituent groups are fluorine, chlorine, bromine, methoxy, ester group and p-trifluoromethyl; r¹Is methyl or hydrogen.

5. The process for producing an epsilon-, zeta-, eta-cyano carboxylic acid compound as recited in claim 1, wherein: the cyclic ketoxime has the following structural formula:

wherein R is on a cyclic ketoxime³、R⁴、R⁵One selected from aryl, methyl, cyano, benzyl and ester; x is C, O, N; r²＝p-CF₃C₆H₄CO，n＝1，2，3。

6. The process for producing an epsilon-, zeta-, eta-cyano carboxylic acid compound as recited in claim 1, wherein: the photocatalyst is bis [2- (2, 4-difluorophenyl) -5-trifluoromethylpyridine ] [2-2 '-bi (4-tert-butylpyridinium) ] iridium bis (hexafluorophosphate) salt, tris (2,2' -bi-pyridine) ruthenium bis (hexafluorophosphate) salt, 2,4,5, 6-tetra (9-carbazolyl) -isophthalonitrile, and the using amount of the catalyst is 2 mol% of the mole number of the olefin.

7. The process for producing an epsilon-, zeta-, eta-cyano carboxylic acid compound as recited in claim 1, wherein: the reducing agent is DIPEA or triethylamine, and the molar ratio of the reducing agent to the olefin is 3.0: 1.

8. the process for producing an epsilon-, zeta-, eta-cyano carboxylic acid compound as recited in claim 2, wherein: the molar ratio of methyl iodide to olefin is 4: 1.

Technical Field

The invention relates to the fields of medicine, organic chemical industry and fine chemical industry, in particular to a method for simply and efficiently synthesizing an epsilon-, zeta-, eta-cyano carboxylic acid compound by using iridium, 4CZIPN or ruthenium as a raw material, using carbon dioxide, olefin and cyclic ketoxime as a reducing agent, using DIPEA or triethylamine as a solvent and using DMSO as a solvent.

Background

Cyanocarboxylic acids are an important class of biologically active compounds and are also important intermediates in the construction of pharmaceutical molecules such as vitamin B6, caffeine, folic acid (see (a) Oliver, L.; Jens-Uwe, R.; Hilke-Marie, L.; Paul, H.; Constantze, M.preparation cyano carboxylic acid esters, EP 2455365A1,20120523; B) Michael Paul, B.; John Wing, W.biocatalytic prediction of 1-cyanocyclohexaacetic acid, WO 2004111256A1,20041223.). In addition, a cyano group in the structure can be hydrolyzed into a carboxyl group, and the obtained aliphatic dicarboxylic acid compound has wide application in high-molecular polymerization reaction and is an important monomer for synthesizing polyamide and polyester, so that the effective synthesis of the compound has strong application value (see: Ren, W.; Chu, J.; Sun, F.; Shi, Y.Org.Lett.2019,21, 5967; (b) Yang, J.; Liu, J.; Ge, Y.; Huang, W.; Neumann, H.; Jacksell, R.; Beller, M.Angew.Chem.int.Ed.2020,59, 20394;). The classical synthesis method of the compound is prepared by utilizing nucleophilic substitution reaction of halogenated carboxylic acid and sodium cyanide or hydrocyanic acid, however, the method needs to use virulent sodium cyanide or hydrocyanic acid, and brings great trouble to actual operation; in addition, the hydrolysis reaction of a single cyano group of a dinitrile compound is also an important method for preparing cyano carboxylic acid, however, two cyano groups in the compound have similar reaction activities, and how to control reaction conditions to ensure that only one cyano group is hydrolyzed is challenging work (see: Zhu, d.; MukherJee, c.; Biehl, e.r.; Hua, l.adv.synth.catl.2007, 349, 1667-1670.).

Recently, professor da reports that a series of cyano carboxylic acids can be obtained through a ring-opening carboxylation reaction of cyclic ketoxime ester and carbon dioxide, but the reaction is limited to 2-aryl substituted cyclic ketoxime ester, the substrate application range is narrow, and the synthesis difficulty of the substrate is large (see: Jiang, Y. -X.; Chen, L.; Ran, C. -K.; Song, L.; Zhang, W.; Liao, L.; Yu D. -G. Chem 2020,13, 6312-6317). The method further develops the method for rapidly constructing the cyano carboxylic acid compounds with different carbon chain lengths by using simple and easily-obtained raw materials and mild reaction conditions, and has higher research value.

Disclosure of Invention

In view of the defects in the background art, the invention synthesizes a series of epsilon-, zeta-, eta-cyano carboxylic acids by using cheap and easily available carbon dioxide, olefin and cyclic ketoxime (2-position, 3, 3-position substituted cyclobutanone oxime, cyclopentanone oxime, cyclohexanone oxime and the like) as starting materials and through continuous free radical addition/single electron reduction/carboxylation reaction under the catalysis of iridium, 4CZIPN or ruthenium and the promotion of visible light. The method has the advantages of wide raw material source, simple and convenient operation method, easy separation and purification and higher yield.

The synthesis method of the epsilon-, zeta-, eta-cyano carboxylic acid compound comprises the following steps: olefin and cyclic ketoxime are used as raw materials, iridium, 4CZIPN or ruthenium are used as a photocatalyst, dimethyl sulfoxide is used as a solvent in the presence of a reducing agent, and carbon dioxide gas is introduced after all the raw materials participating in the reaction are added for reaction to obtain a series of cyano carboxylic acid compounds.

The specific process of the reaction is as follows:

r' on the olefin is phenyl, methyl, naphthyl, thienyl or hydrogen; when R' and R are phenyl, the substituent groups are fluorine, chlorine, bromine, methoxy, ester group and p-trifluoromethyl; r¹Is methyl or hydrogen.

The structural formula of the used raw material olefin is as follows:r' on the olefin, R is phenylMethyl, naphthyl, thienyl or hydrogen; when R' and R are phenyl, the substituent groups are fluorine, chlorine, bromine, methoxy, ester group and p-trifluoromethyl; r¹Is methyl or hydrogen.

The cyclic ketoxime is selected from four-membered ring, six-membered ring, heterocyclic ring and different substituent products carried by the same.

The structural formula of the used raw material cyclic ketoxime is as follows:r on cyclic ketoximes³、R⁴、R⁵One selected from aryl, methyl, cyano, benzyl and ester; x is C, O, N; r²＝p-CF₃C₆H₄CO，n＝1，2，3。

The specific reaction conditions of the invention are as follows: and (3) adding a 2x3W blue LED into an oil bath kettle at 50 ℃ for reacting for 1 hour after the room temperature is 12-24 hours.

The photocatalyst used in the reaction is bis [2- (2, 4-difluorophenyl) -5-trifluoromethylpyridine ] [2-2 '-bi (4-tert-butylpyridine) ] iridium bis (hexafluorophosphate) salt, tris (2,2' -bipyridyl) ruthenium bis (hexafluorophosphate) salt, 2,4,5, 6-tetra (9-carbazolyl) -isophthalonitrile, and the amount of the catalyst is 2 mol% of the mole number of the olefin;

the molar ratio of the olefin to the cyclic ketoxime used is 1: 1.5, the pressure of the carbon dioxide is 0.1 MPa;

the reducing agent is N, N-Diisopropylethylamine (DIPEA) or triethylamine (Et)₃N); its molar ratio to olefin was 3.0: 1.

the molar ratio of methyl iodide to olefin is 4: 1.

the post-treatment of the reaction is simple and convenient, and the pure epsilon-, zeta-, eta-cyano carboxylic acid compound can be obtained by only using a simple column chromatography separation method and using a mixed solvent of petroleum ether and ethyl acetate as an eluent.

The raw materials of the olefin and the cyclic ketoxime adopted by the invention are synthesized according to the literature (Cheng, Z.; Jin, W.; Liu, C.B.)₂pin₂-catalyzed oxidative cleavage of a C＝C double bond with molecular oxygen,Org.Chem.Front.2019,6,841-845；Zhao,B.；Shi,Z.Angew.Chem.Int.Ed.2017,56,12727–12731.)。

Has the advantages that:

the invention provides a more concise and feasible way for synthesizing a series of epsilon-, zeta-, eta-cyano carboxylic acid compounds by using the olefin and the cyclic ketoxime for the first time, and has important application value.

Detailed Description

The present invention is described in detail below with reference to examples, which are set forth below:

example 16 methyl cyano-2, 2-diphenylhexanoate

Methyl 6-cyano-2,2-diphenylhexanoate

1, 1-stilbene (0.2mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol) and Ir [ (dF (CF)₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 76% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.34–7.28(m,10H),3.71(s,3H),2.43–2.38(m,2H),2.27(t,J＝7.2Hz,2H),1.68-1.60(m,2H),1.26-1.19(m,2H).¹³C NMR(101MHz,CDCl₃) δ 174.5,142.4,128.7,127.9,126.9,119.5,60.1,52.4,37.3,29.6,25.7,24.5,16.8. mass spectrometry data: MS (EI) 307.2 (M)⁺)。

Example 26 methyl cyano-2-phenyl-2- (p-tolyl) hexanoate

Methyl 6-cyano-2-phenyl-2-(p-tolyl)hexanoate

1-methyl-4- (1-phenylvinyl) benzene (0.2mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol), Ir [ (dF (CF)₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 60% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl3)δ7.28–7.19(m,6H),7.11–7.06(m,4H),3.64(s,3H),2.35-2.32(m,2H),2.30(s,3H),2.22(t,J＝7.3Hz,2H),1.62–1.55(m,2H),1.20–1.14(m,2H).¹³c NMR (101MHz, CDCl3)) delta 174.64,142.61,139.38,136.53,128.66,128.63,128.56,127.88,126.79,119.53,59.78,52.35,37.33,25.78,24.56,20.89,16.87 mass spectral data: MS (EI) 321.2 (M)⁺)。

Example 3: 6-cyano-2- (4-methoxyphenyl) -2-phenylhexanoic acid methyl ester

Methyl 6-cyano-2-(4-methoxyphenyl)-2-phenylhexanoate

1-methoxy-4- (1-phenylvinyl) benzene (0.2mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol), Ir [ (dF: (b) (b))CF₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 68% yield. Nuclear magnetic data:¹H NMR(400MH z,CDCl₃)δ7.36–7.26(m,5H),7.24–7.21(m,2H),6.90–6.86(m,2H),3.84(s,3H),3.73(s,3H),2.42–2.37(m,2H),2.30(t,J＝7.3Hz,2H),1.70–1.63(m,2H),1.27–1.20(m,2H).¹³C NMR(101MHz,CDCl₃) δ 174.7,158.3,142.8,134.3,129.8,128.6,127.9,126.8,119.5,113.2,59.4,55.1,52.3,37.4,25.8,24.6,16.9. mass spectrometry data: MS (EI) 337.2 (M)⁺)。

Example 4: 6-cyano-2- (4-fluorophenyl) -2-phenylhexanoic acid methyl ester

Methyl 6-cyano-2-(4-fluorophenyl)-2-phenylhexanoate

1-fluoro-4- (1-phenylvinyl) benzene (0.2mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol), Ir [ (dF (CF)₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and thenThe reaction mixture was diluted with brine and Extracted (EA) with ethyl acetate at least 6 times (2mL × 6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to afford the desired product in 56% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl3)δ7.33–7.26(m,3H),7.24–7.20(m,4H),6.98(t,J＝8.7Hz,2H),3.67(s,3H),2.38–2.34(m,2H),2.27(t,J＝7.2Hz,2H),1.66–1.59(m,2H),1.26–1.16(m,2H).¹³c NMR (101MHz, CDCl3) delta 174.3,142.3,130.4,130.4,128.5,128.1,127.0,114.9,114.6,59.6,52.5,37.4,25.7,24.5,16.9 mass spectral data: MS (EI) 325.2 (M)⁺)。

Example 5: 2- (4-chlorophenyl) -6-cyano-2-phenylhexanoic acid methyl ester

Methyl 2-(4-chlorophenyl)-6-cyano-2-phenylhexanoate

1-chloro-4- (1-phenylvinyl) benzene (0.2mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol), Ir [ (dF (CF)₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 59% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.34–7.27(m,5H),7.24–7.19(m,4H),3.70(s,3H),2.37(t,J＝8.1Hz,2H),2.28(t,J＝7.2Hz,2H),1.68–1.61(m,2H),1.27–1.18(m,2H).¹³C NMR(101MHz,CDCl₃) δ 174.1,142.1,141.1,132.8,130.2,128.5,128.1,128.1,127.1,119.4,59.7,52.5,37.2,25.7,24.5,16.9. mass spectrometry data: MS (EI) 341.1 (M)⁺)。

Example 6: 2- (4-bromophenyl) -6-cyano-2-phenylhexanoic acid methyl ester

Methyl 2-(4-bromophenyl)-6-cyano-2-phenylhexanoate

1-bromo-4- (1-phenylvinyl) benzene (0.2mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol), Ir [ (dF (CF)₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 83% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.44(d,J＝8.6Hz,2H),7.35–7.28(m,4H),7.23(d,J＝7.0Hz,3H),7.15(d,J＝8.6,2H),3.71(s,3H),2.37(t,J＝8.1Hz,2H),2.29(t,J＝7.2Hz,2H),1.68–1.61(m,2H),1.24–1.15(m,2H).¹³C NMR(101MHz,CDCl₃) δ 173.9,141.9,141.6,131.0,130.5,128.4,128.1,127.1,121.0,119.4,59.7,52.5,37.1,25.6,24.5,16.8. mass spectrometry data: MS (EI) 385.1 (M)⁺)。

Example 7: 6-cyano-2-phenyl-2- (4- (trifluoromethyl) phenyl) hexanoic acid methyl ester

Methyl 6-cyano-2-phenyl-2-(4-(trifluoromethyl)phenyl)hexanoate

1- (1-Phenylvinyl) -4- (trifluoromethyl) benzene (0.2mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol), Ir [ (dF (CF)₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 44% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.52(d,J＝8.4Hz,2H),7.34(d,J＝8.2Hz,2H),7.31–7.27(m,2H),7.26–7.22(m,1H),7.20–7.17(m,2H),3.67(s,3H),2.39–2.34(m,2H),2.24(t,J＝7.2Hz,2H),1.65–1.57(m,2H),1.19–1.12(m,2H).¹³C NMR(101MHz,CDCl₃) δ 173.8,141.7,129.2,128.5,128.2,127.3,124.9,124.8,119.4,60.1,52.6,37.2,25.7,24.5,16.9. mass spectrometry data: MS (EI) 375.1 (M)⁺)。

Example 8: 6-cyano-2-phenyl-2- (m-tolyl) hexanoic acid methyl ester

Methyl 6-cyano-2-phenyl-2-(m-tolyl)hexanoate

1-methyl-3- (1-phenylvinyl) benzene (0.2mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol), Ir [ (dF (CF)₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. Will be provided withThe reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 59% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.33–7.18(m,6H),7.07(t,J＝10.4Hz,3H),3.70(s,3H),2.40–2.34(m,2H),2.33(s,3H),2.27(t,J＝7.3Hz,2H),1.67–1.59(m,2H),1.27–1.17(m,2H).¹³C NMR(101MHz,CDCl₃) δ 174.6,142.5,142.4,137.5,129.2,128.7,127.9,127.8,127.6,126.9,125.8,119.5,60.0,52.3,37.3,25.8,24.6,21.6,16.8. mass spectrometry data: MS (EI) 321.2 (M)⁺)。

Example 9: 2- (2-chlorophenyl) -6-cyano-2-phenylhexanoic acid methyl ester

Methyl 2-(2-chlorophenyl)-6-cyano-2-phenylhexanoate

1-chloro-2- (1-phenylvinyl) benzene (0.2mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol), Ir [ (dF (CF)₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Drying and reducingConcentrating under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 66% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.3–7.30(m,3H),7.26–7.22(m,5H),7.17–7.13(m,1H),3.71(s,3H),2.39–2.35(m,2H),2.28(t,J＝7.2Hz,2H),1.68–1.61(m,2H),1.23–1.14(m,2H).¹³C NMR(101MHz,CDCl₃) δ 174.1,140.2,134.1,131.0,130.9,128.9,128.3,128.1,127.3,126.1,59.2,52.5,33.1,25.6,24.2,16.9. mass spectrometry data: MS (EI) 282.1 (M)⁺)。

Example 10: 6-cyano-2- (2, 4-dichlorophenyl) -2-phenylhexanoic acid methyl ester

Methyl 6-cyano-2-(2,4-dichlorophenyl)-2-phenylhexanoate

2, 4-dichloro-1- (1-phenylvinyl) benzene (0.2mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol), Ir [ (dF (CF)₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 67% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.44(d,J＝7.4Hz,2H),7.40(d,J＝2.2Hz,1H),7.38–7.28(m,3H),7.16(dd,J＝8.6,2.2Hz,1H),7.00(d,J＝8.6Hz,1H),3.66(s,3H),2.69–2.61(m,1H),2.54–2.46(m,1H),2.35–2.21(m,2H),1.75–1.56(m,2H),1.43–1.33(m,1H),0.96–0.86(m,1H).¹³CNMR(101MHz,CDCl₃)δ173.7,139.0,138.9,134.8,133.4,131.9,130.6,128.8,128.3,127.5,126.4,119.3,58.9,52.6,33.1,25.6,24.2,16.9. mass spectrometry data: MS (EI) 375.1 (M)⁺)。

Example 11: 6-cyano-2, 2-di-p-tolylhexanoic acid methyl ester

Methyl 6-cyano-2,2-di-p-tolylhexanoate

4,4' - (ethylene-1, 1-diyl) bis (toluene) (0.2mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol) and Ir [ (dF (CF)₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 62% yield. Nuclear magnetic data:¹H NMR(400MH z,CDCl3)δ7.15-7.13(m,2H),7.12-7.13(d,J＝2.9Hz,6H),7.10(s,1H),3.68(s,3H),2.37(s,1H),2.34(s,6H),2.32(s,1H),2.28(s,2H),1.63(t,J＝7.6Hz,2H),1.25–1.20(m,2H).¹³c NMR (101MHz, CDCl3) delta 174.8,139.5,136.4,128.6,128.5,119.6,77.3,77.00,76.7,59.5,52.3,37.4,25.8,24.6,20.9,16.9 mass spectral data: MS (EI) 335.2(M +).

Example 12: 2, 2-bis (4-chlorophenyl) -6-cyanohexanoic acid methyl ester

Methyl 2,2-bis(4-chlorophenyl)-6-cyanohexanoate

4,4' - (ethylene-1, 1-diyl) bis (chlorobenzene) (0.2mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol) and Ir [ (dF (CF)₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 33% yield. Nuclear magnetic data:¹H NMR(400MH z,CDCl₃)δ7.30–7.26(m,4H),7.17–7.14(m,4H),3.69(s,3H),2.34–2.26(m,4H),1.64(t,J＝7.5Hz,2H),1.25–1.17(m,2H).¹³C NMR(101MHz,CDCl₃) δ 173.7,140.7,133.1,130.0,128.3,119.4,59.3,52.7,37.2,25.7,24.5,16.9. mass spectrometry data: MS (EI) 375.1 (M)⁺)。

Example 13: 6-cyano-2- (naphthalen-2-yl) -2-phenylhexanoic acid methyl ester

Methyl 6-cyano-2-(naphthalen-2-yl)-2-phenylhexanoate

2- (1-Phenylvinyl) naphthalene (0.2mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol) and Ir [ (dF (CF)₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Then, mixing the mixture to the reactionMeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 82% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.71–7.68(m,3H),7.64(d,J＝8.8Hz,1H),7.36(d,J＝9.8Hz,2H),7.22–7.16(m,6H),3.60(s,3H),2.44–2.32(m,2H),2.13(t,J＝7.3Hz,2H),1.57–1.49(m,2H),1.18–1.12(m,2H).¹³C NMR(101MHz,CDCl₃) δ 174.3,142.4,139.7,132.7,132.1,128.7,128.1,128.0,127.5,127.3,127.2,127.1,126.9,126.1,126.1,119.5,60.1,52.4,37.20,25.7,24.6,16.8. mass spectrometry data: MS (EI) 357.2 (M)⁺)。

Example 14: 6-cyano-2-phenyl-2- (thien-2-yl) hexanoic acid methyl ester

Methyl 6-cyano-2-phenyl-2-(thiophen-2-yl)hexanoate

2- (1-Phenylvinyl) thiophene (0.2mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol), Ir [ (dF (CF)₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 56% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.34–7.27(m,4H),7.25(d,J＝6.7Hz,2H),6.98(t,J＝4.7Hz,2H),3.75(s,3H),2.51–2.36(m,2H),2.29(t,J＝7.2Hz,2H),1.70–1.62(m,2H),1.40–1.30(m,2H).¹³C NMR(101MHz,CDCl₃) δ 173.6,145.8,142.8,128.1,127.4,127.2,127.0,126.2,125.1,119.4,57.8,52.6,39.1,25.6,24.6,16.9. mass spectrometry data: MS (EI) 313.1 (M)⁺)。

Example 15: (R) -6-cyano-3-methyl-2, 2-diphenylhexanoic acid methyl ester

Methyl(R)-6-cyano-3-methyl-2,2-diphenylhexanoate

1-methyl-2, 2-diphenylethylene (0.2mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol) and Ir [ (dF (CF)₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 14% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.31–7.24(m,11H,overlapped with CDCl₃),3.62(s,3H),3.14–3.06(m,1H),2.34–2.29(m,2H),1.77–1.66(m,4H),0.85(d,J＝6.6Hz,3H).¹³C NMR(101MHz,CDCl₃) δ 174.6,127.5,126.9,126.9,119.6,65.6,52.3,35.5,29.7,24.0,17.3. mass spectrometry data: MS (EI) 321.2 (M)⁺)。

Example 16: 6-cyano-2-methyl-2- (naphthalen-2-yl) hexanoic acid methyl ester

Methyl 6-cyano-2-methyl-2-(naphthalen-2-yl)hexanoate

2- (1-methylvinyl) naphthalene (0.2mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol), Ir [ (dF (CF)₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). Then, the Sch lenk tube was stirred at room temperature under 2X3W blue LED irradiation for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 25% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.84–7.79(m,3H),7.72(d,J＝2.0Hz,1H),7.50–7.45(m,2H),7.40(dd,J＝8.8,2.0Hz,1H),3.67(s,3H),2.33–2.29(m,2H),2.17–2.00(m,2H),1.69(s,3H),1.67–1.63(m,2H),1.40–1.30(m,2H).¹³C NMR(101MHz,CDCl₃) δ 176.5,140.5,133.2,132.2,128.2,128.0,127.4,126.2,126.0,124.4,124.3,119.5,52.3,50.1,38.4,25.8,23.9,22.4,17.0. mass spectrometry data: MS (EI) 295.2 (M)⁺)。

Example 17: (S) -4- (6-cyano-1-methoxy-1-oxohex-2-yl) benzoic acid methyl ester

Methyl(S)-4-(6-cyano-1-methoxy-1-oxohexan-2-yl)benzoate

Methyl 4-vinylbenzoate (0.2mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol) and Ir [ (dF (CF)₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 72% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.98(d,J＝8.4Hz,2H),7.34(d,J＝8.4Hz,2H),3.89(s,3H),3.65(s,3H),3.59(t,J＝7.6Hz,1H),2.30(t,J＝7.1Hz,2H),2.16–2.07(m,1H),1.82–1.76(m,1H),1.69–1.63(m,2H),1.44–1.33(m,2H).¹³C NMR(101MHz,CDCl₃) δ 173.4,166.7,143.6,130.0,129.3,127.8,119.3,52.2,52.1,51.2,32.4,26.5,25.0,16.9. mass spectrometry data: MS (EI) 289.1 (M)⁺)。

Example 18: 5- (cyanomethyl) -2, 2-diphenyladipic acid dimethyl ester

Dimethyl 5-(cyanomethyl)-2,2-diphenylhexanedioate

1, 1-stilbene (0.2mmol), methyl 3- (((4- (trifluoromethyl) benzoyl) oxy) imino) cyclobutane-1-carboxylate (0.3mmol), Ir [ (dF (CF)₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction was carried outThe mixture was diluted with brine and Extracted (EA) at least 6 times with ethyl acetate (2mL × 6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 60% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.30(dd,J＝14.2,6.6Hz,6H),7.25–7.21(m,4H),3.71(s,3H),3.69(s,3H),2.70–2.57(m,2H),2.51–2.40(m,2H),2.37–2.29(m,1H),1.59–1.40(m,2H).¹³C NMR(101MHz,CDCl₃) δ 172.7,142.1,142.0,128.6,128.6,128.0,127.0,59.9,52.5,52.3,41.6,34.9,27.2,19.1. mass spectrometry data: MS (EI) 365.2 (M)⁺)。

Example 19: 6-cyano-2, 2, 5-triphenylhexanoic acid methyl ester

Methyl 6-cyano-2,2,5-triphenylhexanoate

1, 1-stilbene (0.2mmol), 3-phenylcyclobutane-1-one O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol), Ir [ (dF (CF) was added₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 77% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.35–7.28(m,9H),7.20(d,J＝7.4Hz,4H),7.10(d,J＝7.0Hz,2H),3.67(s,3H),2.89–2.81(m,1H),2.49(d,J＝7.0Hz,2H),2.40–2.33(m,1H),2.24–2.17(m,1H),1.68–1.52(m,2H).¹³C NMR(101MHz,CDCl₃) δ 174.4,142.3,142.2,141.0,128.7,128.6,127.9,127.9,127.4,127.2,126.9,126.8,118.2,60.0,52.3,42.4,35.7,30.2,25.3. mass spectrometry data: MS (EI) 383.2 (M)⁺)。

Example 20: 5-benzyl-6-cyano-2, 2-diphenylhexanoic acid methyl ester

Methyl 5-benzyl-6-cyano-2,2-diphenylhexanoate

1, 1-stilbene (0.2mmol), 3-benzylcyclobutane-1-one O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol), Ir [ (dF (CF) in₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 71% yield. Nuclear magnetic data:¹H NMR(400MHz,CDC l₃)δ7.28(t,J＝7.1Hz,4H),7.25–7.18(m,9H),7.06(d,J＝6.7Hz,2H),3.67(s,3H),2.73(dd,J＝13.8,5.6Hz,1H),2.52–2.39(m,3H),2.23(dd,J＝16.8,5.4Hz,1H),2.13(dd,J＝16.9,5.6Hz,1H),1.90–1.86(m,1H),1.29–1.25(m,2H).¹³C NMR(101MHz,CDCl₃) δ 174.4,142.4,142.3,138.6,128.9,128.7,128.6,128.5,127.9,127.9,126.9,126.9,126.4,118.3,60.1,52.4,39.4,37.7,35.5,29.0,20.9. mass spectrometry data: MS (EI) 397.2 (M)⁺)。

Example 21: 5- (benzyloxy) -6-cyano-2, 2-diphenylhexanoic acid methyl ester

Methyl 5-(benzyloxy)-6-cyano-2,2-diphenylhexanoate

1, 1-stilbene (0.2mmol), 3-benzyloxycyclobutane-1-one O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol), Ir [ (dF (CF) in₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 50% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.24–7.10(m,15H),4.38(q,J＝11.6Hz,2H),3.57(s,3H),3.52–3.45(m,1H),2.36(d,J＝5.9Hz,2H),2.25–2.17(m,1H),1.39–1.23(m,2H),1.15–1.08(m,1H).¹³C NMR(101MHz,CDCl₃) δ 174.4,142.4,142.1,137.4,128.8,128.7,128.4,128.0,127.9,127.8,127.0,126.9,117.5,74.4,71.6,59.9,52.4,33.1,29.5,22.8. mass spectrometry data: MS (EI) 413.2 (M)⁺)。

Example 22: 5- (((benzyloxy) carbonyl) amino) -6-cyano-2, 2-diphenylhexanoic acid methyl ester

Methyl 5-(((benzyloxy)carbonyl)amino)-6-cyano-2,2-diphenylhexanoate

Benzyl 1, 1-stilbene (0.2mmol), (3- (((4- (trifluoromethyl) benzoyl) oxy) imino) cyclobutyl) carbamate (0.3mmol), Ir [ (dF (CF)₃)ppy)]₂(dtbbpy)·PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 39% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.36–7.27(m,12H),7.24–7.18(m,3H),5.14–5.08(m,4H),3.70(s,3H),2.78–2.64(m,1H),2.56–2.44(m,2H),2.37–2.31(m,1H),1.33(d,J＝6.9Hz,2H).¹³C NMR(101MHz,CDCl₃) δ 174.4,155.8,142.3,142.1,136.0,128.6,128.6,128.5,128.5,128.2,128.2,128.1,128.1,128.1,128.0,127.1,127.1,117.0,66.9,59.9,52.6,48.2,43.6,34.6,29.5,25.0,23.8,19.4. mass spectrometry data: MS (EI) 456.2 (M)⁺)。

Example 23: 5, 6-dicyano-2, 2-diphenylhexanoic acid methyl ester

Methyl 5-(((benzyloxy)carbonyl)amino)-6-cyano-2,2-diphenylhexanoate

1, 1-stilbene (0.2mmol), 3-cyanocyclobutane-1-one O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol), Ir [ (dF (CF) in₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, and the reaction was carried outThe mixture was stirred at 50 ℃ for about 1 hour, then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2mL × 6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 80% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.33–7.28(m,6H),7.23(d,J＝1.8Hz,1H),7.22–7.19(m,3H),3.68(s,3H),2.77–2.73(m,1H),2.59(dd,J＝6.8,4.0Hz,2H),2.49–2.42(m,1H),1.54–1.48(m,3H).¹³C NMR(101MHz,CDCl₃) δ 174.0,141.7,141.7,128.5,128.5,128.2,128.2,127.3,118.7,115.4,59.7,52.6,35.3,28.6,27.7,20.7. mass spectrometry data: MS (EI) 332.2 (M)⁺)。

Example 24: 6-cyano-5-methyl-2, 2, 5-triphenylhexanoic acid methyl ester

Methyl 6-cyano-5-methyl-2,2,5-triphenylhexanoate

1, 1-stilbene (0.2mmol), 3-methyl-3-phenylcyclobutane-1-one O- (4- (trifluoromethyl) benzyl) oxime (0.3mmol), Ir [ (dF (CF) in₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 70% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.35–7.28(m,9H),7.19–7.16(m,4H),7.13(d,J＝7.4Hz,2H),3.67(s,3H),2.62–2.51(m,2H),2.30–2.22(m,1H),2.10–2.01(m,1H),1.73–1.65(m,1H),1.56(dd,J＝12.7,4.2Hz,1H),1.51(s,3H).¹³C NMR(101MHz,CDCl₃) δ 174.3,143.4,142.3,142.2,128.7,128.7,128.5,127.9,127.9,126.8,126.7,125.7,117.8,59.8,52.3,40.0,36.4,32.7,31.7,24.8. mass spectrometry data: MS (EI) 397.2 (M)⁺)。

Example 25: 4- (cyanomethyl) -4- (4-methoxy-4-oxo-3, 3-diphenylbutyl) piperidine-1-carboxylic acid tert-butyl ester

tert-Butyl4-(cyanomethyl)-4-(4-methoxy-4-oxo-3,3-diphenylbutyl)piperidine-1-carboxylate

Stilbene (0.2mmol), 2- (((4- (trifluoromethyl) benzoyl) oxy) imino) -7-azaspiro [ 3.5%]Nonane-7-carboxylic acid tert-butyl ester (0.3mmol), Ir [ (dF (CF)₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 76% yield. Nuclear magnetic data:¹H NM R(400MHz,CDCl₃)δ7.29(d,J＝8.8Hz,3H),7.24–7.21(m,7H),3.66(s,3H),3.38–3.35(m,2H),3.06–2.99(m,2H),2.32–2.26(m,4H),1.43–1.41(m,4H),1.39(s,9H),1.25–1.21(m,2H).¹³C NMR(101MHz,CDCl₃) δ 174.2,154.5,142.2,128.6,128.0,127.0,117.3,79.6,59.9,52.4,34.1,31.7,30.9,28.3,26.3. mass spectrometry data: MS (EI) 476.3 (M)⁺)。

Example 26: 6-cyano-4-methyl-2, 2-diphenylhexanoic acid methyl ester

Methyl 6-cyano-2,2,4-triphenylhexanoate

1, 1-stilbene (0.2mmol), 2-methylcyclobutan-1-one O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol), Ir [ (dF (CF)₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 78% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.34–7.26(m,10H),3.68(s,3H),2.35(t,J＝5.1Hz,2H),2.26–2.08(m,2H),1.45–1.38(m,1H),1.28(dd,J＝7.5Hz,2H),0.63(d,J＝6.7Hz,3H).¹³C NMR(101MHz,CDCl₃) δ 174.5,143.1,142.9,128.9,128.8,128.0,127.9,127.0,126.9,119.7,60.0,52.3,44.7,33.2,29.4,20.2,14.7. mass spectrometry data: MS (EI) 321.2 (M)⁺)。

Example 27: 6-cyano-2, 2, 4-triphenylhexanoic acid methyl ester

Methyl 6-cyano-2,2,4-triphenylhexanoate

1, 1-stilbene (0.2mmol), 2-phenylcyclobutane-1-one O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol), Ir [ (dF (CF) was added₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 19% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.34–7.26(m,10H),3.68(s,3H),2.35(t,J＝5.1Hz,2H),2.26–2.08(m,2H),1.45–1.38(m,1H),1.28(dd,J＝7.5Hz,2H),0.63(d,J＝6.7Hz,3H).¹³C NMR(101MHz,CDCl₃) δ 174.5,143.1,142.9,128.9,128.8,128.0,127.9,127.0,126.9,119.7,60.0,52.3,44.7,33.2,29.4,20.2,14.7. mass spectrometry data: MS (EI) 378(M +);

example 28: 4- (Cyanomethoxy) -2, 2-diphenylbutyric acid methyl ester

Methyl 4-(cyanomethoxy)-2,2-diphenylbutanoate

1, 1-stilbene (0.2mmol), 3-oxocyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol) and Ir [ (dF (CF)₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 66% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.32–7.28(m,6H),7.25–7.23(m,4H),4.07(s,2H),3.69(s,3H),3.36(t,J＝7.1Hz,2H),2.73(t,J＝7.2Hz,2H).¹³C NMR(101MHz,CDCl₃) δ 174.1,142.1,128.5,128.1,127.1,115.8,69.0,58.2,56.1,52.5,37.3. mass spectrometry data: MS (EI) 309.1 (M)⁺)。

Example 29: 4- ((tert-Butoxycarbonyl) (cyanomethyl) amino) -2, 2-diphenylbutyric acid methyl ester

Methyl 4-((tert-butoxycarbonyl)(cyanomethyl)amino)-2,2-diphenylbutanoate

1, 1-stilbene (0.2mmol), 3- (((4- (trifluoromethyl) benzoyl) oxy) imino) azetidine-1-carboxylic acid tert-butyl ester (0.3mmol), Ir [ (dF (CF3) ppy)]2 (dtbbpy). PF6(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 74% yield. Nuclear magnetic data:¹H NM R(400MHz,CDCl3)δ7.33–7.28(m,6H),7.25–7.23(m,4H),4.03(d,J＝50.8Hz,2H),3.71(s,3H),3.07–3.03(m,2H),2.62(s,2H),1.46(s,3H),1.37(s,6H).¹³c NMR (101MHz, CDCl3) delta 174.1,154.4,141.9,128.5,128.2,127.2,116.2,81.5,58.7,52.6,45.4,36.1,35.2,28.1 Mass SpectrometryData: MS (EI) 408.2 (M)⁺)。

Example 30: 4- (Cyanomethoxy) -2, 2-diphenylbutyric acid methyl ester

Methyl 4-(2-cyanoethoxy)-2,2-diphenylpentanoate

1, 1-stilbene (0.2mmol), 2-methyldihydrofuran-3 (2H) -one-O- - (4- (trifluoromethyl) benzoyl) oxime (0.3mmol) and Ir [ (dF (CF)₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 59% yield. Nuclear magnetic data¹H NMR(400MHz,CDCl₃)δ7.36(d,J＝7.6Hz,2H),7.31–7.28(m,6H),7.24–7.20(m,2H),3.65(s,3H),3.57–3.51(m,1H),3.10–3.05(m,2H),2.99–2.93(m,1H),2.43–2.37(m,2H),2.29(dd,J＝13.9,3.1Hz,1H),1.09(d,J＝6.0Hz,3H).¹³C NMR(101MHz,CDCl₃) δ 174.5,143.6,142.9,129.2,128.3,128.0,127.6,126.8,126.5,117.9,73.1,62.6,57.9,52.1,45.6,19.5,18.7. mass spectrometry data: MS (EI) 337.2 (M)⁺)。

Example 31: 3- ((3-Cyanomethyl) -1,2, 2-trimethylcyclopentyl) -2, 2-diphenylpropanoic acid methyl ester

Methyl 3-(3-(cyanomethyl)-1,2,2-trimethylcyclopentyl)-2,2-diphenylpropanoate

1, 1-stilbene (0.2mmol) and 1,7, 7-trimethylbicyclo [2.2.0 ]]heptane-O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol), Ir [ (dF (CF)₃)ppy)]₂(dtbbpy)PF₆(2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 21% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.44(d,J＝7.0Hz,2H),7.38(d,J＝7.0Hz,2H),7.27–7.25(m,3H),7.23–7.20(m,4H,overlapped with CDCl₃),3.64(s,3H),2.65(d,J＝13.8Hz,1H),2.52(d,J＝13.8Hz,1H),2.39–2.34(m,1H),2.25–2.19(m,1H),2.17–2.11(m,1H),1.82–1.77(m,1H),1.25–1.11(m,2H),1.04(s,3H),0.82–0.77(m,1H),0.72(s,3H),0.46(s,3H).¹³C NMR(101MHz,CDCl₃) δ 174.5,145.2,144.6,129.1,128.9,127.8,127.8,126.6,126.6,120.0,57.1,52.1,47.6,46.8,44.1,44.0,32.7,28.7,23.5,20.3,19.7,18.7. mass spectrometry data: MS (EI) 389.2 (M)⁺)。

Example 32: 8-cyano-2, 2, 4-triphenyloctanoic acid methyl ester

Methyl 8-cyano-2,2,4-triphenyloctanoate

1, 1-stilbene (0.2mmol), 2-phenylcyclohexanone-O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol), Ir [ (dF (CF)₃)ppy)]₂(dtbbpy)PF₆(2mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 21% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.44(d,J＝7.0Hz,2H),7.38(d,J＝7.0Hz,2H),7.27–7.25(m,3H),7.23–7.20(m,4H,overlapped with CDCl₃),3.64(s,3H),2.65(d,J＝13.8Hz,1H),2.52(d,J＝13.8Hz,1H),2.39–2.34(m,1H),2.25–2.19(m,1H),2.17–2.11(m,1H),1.82–1.77(m,1H),1.25–1.11(m,2H),1.04(s,3H),0.82–0.77(m,1H),0.72(s,3H),0.46(s,3H).¹³C NMR(101MHz,CDCl₃) δ 174.5,145.2,144.6,129.1,128.9,127.8,127.8,126.6,126.6,120.0,57.1,52.1,47.6,46.8,44.1,44.0,32.7,28.7,23.5,20.3,19.7,18.7. mass spectrometry data: MS (EI) 389.2 (M)⁺)。

Example 33: 6-cyano-2, 2-diphenylhexanoic acid methyl ester

Methyl 6-cyano-2,2-diphenylhexanoate

1, 1-stilbene (0.2mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol) and Ir [ (dF (CF)₃)ppy)]₂(dtbbpy)PF₆(2mol％,3.4mg)、Et₃N (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Then, turn to the reverseMeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 66% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.34–7.28(m,10H),3.71(s,3H),2.43–2.38(m,2H),2.27(t,J＝7.2Hz,2H),1.68-1.60(m,2H),1.26-1.19(m,2H).¹³C NMR(101MHz,CDCl₃) δ 174.5,142.4,128.7,127.9,126.9,119.5,60.1,52.4,37.3,29.6,25.7,24.5,16.8. mass spectrometry data: MS (EI) 307.2 (M)⁺)。

Example 34: 6-cyano-2, 2-diphenylhexanoic acid methyl ester

Methyl 6-cyano-2,2-diphenylhexanoate

1, 1-stilbene (0.2mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol), 2,4,5, 6-tetrakis (9-carbazolyl) -isophthalonitrile (2 mol%, 3.1mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 53% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.34–7.28(m,10H),3.71(s,3H),2.43–2.38(m,2H),2.27(t,J＝7.2Hz,2H),1.68-1.60(m,2H),1.26-1.19(m,2H).¹³C NMR(101MHz,CDCl₃)δ174.5,142.4,128.7127.9,126.9,119.5,60.1,52.4,37.3,29.6,25.7,24.5,16.8. mass spectrometry data: MS (EI) 307.2 (M)⁺)。

Example 35: 6-cyano-2, 2-diphenylhexanoic acid methyl ester

Methyl 6-cyano-2,2-diphenylhexanoate

1, 1-stilbene (0.2mmol), cyclobutanone O- (4- (trifluoromethyl) benzoyl) oxime (0.3mmol), tris (2,2' -bipyridyl) ruthenium bis (hexafluorophosphate) salt (2 mol%, 3.4mg), DIPEA (0.3mmol) and DMSO (2.0mL) were added to a 20mL Schlenk tube fitted with a Teflon cap. The reaction vessel was evacuated to about-0.1 MPa (last 30 seconds of each time) and backfilled with CO three times₂(1 atmosphere). The Schlenk tube was then stirred at room temperature under 2x3W blue LED illumination for 12 hours. Thereafter, MeI (0.8mmol) was added to the reaction mixture, the reaction mixture was stirred at 50 ℃ for about 1 hour, and then the reaction mixture was diluted with brine and extracted with Ethyl Acetate (EA) at least 6 times (2 mL. times.6). Subsequently, the combined organic layers were passed over anhydrous Na₂SO₄Dried and concentrated under reduced pressure. The residue was purified by flash chromatography on silica gel (PE/EA5/1) to give the desired product in 51% yield. Nuclear magnetic data:¹H NMR(400MHz,CDCl₃)δ7.34–7.28(m,10H),3.71(s,3H),2.43–2.38(m,2H),2.27(t,J＝7.2Hz,2H),1.68-1.60(m,2H),1.26-1.19(m,2H).¹³C NMR(101MHz,CDCl₃) δ 174.5,142.4,128.7,127.9,126.9,119.5,60.1,52.4,37.3,29.6,25.7,24.5,16.8. mass spectrometry data: MS (EI) 307.2 (M)⁺)。