阅读说明：本技术 一种铁催化4-氨基化醇的制备方法 (Preparation method of iron-catalyzed 4-aminoalcohol ) 是由 曾荣 郭秦乐 熊泥 于 2021-08-30 设计创作，主要内容包括：一种铁催化4-氨基化醇的制备方法,包括以下步骤：通过在铁化合物的作用下,提供加热温度和/或光能条件下,在偶氮化合物、添加剂的存在下,相应的有机溶剂中,实现脂肪醇的选择性4-碳氢键断裂、胺化,得到相应的4-氨基醇类化合物,本发明直接利用脂肪醇,选择性地进行碳氢键胺化,具有反应简洁,操作简单、反应时间短、氧化条件温和,原子经济性高、反应产率较高,产物易分离纯化等优点,适用于合成含氨基醇类化合物及其衍生物；可以通过直接利用脂肪族醇作为原料,偶氮化合物廉价易得,避免使用大量重金属盐,在工业生产上非常具有吸引力,同时利用廉价金属进行反应也在金属催化、化学合成、药物修饰等领域具有非常大的应用潜力。(A method of preparing an iron-catalyzed 4-aminoalcohol, comprising the steps of: the method has the advantages of simple reaction, simple operation, short reaction time, mild oxidation condition, high atom economy, high reaction yield, easy separation and purification of products and the like, and is suitable for synthesizing the amino alcohol-containing compound and derivatives thereof; by directly utilizing aliphatic alcohol as a raw material, the azo compound is cheap and easy to obtain, avoids using a large amount of heavy metal salt, is very attractive in industrial production, and has very large application potential in the fields of metal catalysis, chemical synthesis, drug modification and the like by utilizing cheap metal to carry out reaction.)

1. A method for preparing an iron-catalyzed 4-aminoalcohol, comprising the steps of:

under the action of iron compound and under the condition of providing heating temperature and/or light energy, in the presence of azo compound and additive and in organic solvent to implement selective 4-hydrocarbon bond cleavage and amination of fatty alcohol so as to obtain 4-amino alcohol compound, its reaction formula is as follows:

the structural formula of the fatty alcohol is shown asAzo compoundsThe 4-aminoalcohol compound isWherein R, R 'and R' comprise hydrogen, alkyl, substituted or unsubstituted phenyl, naphthyl, pyridine, thiophene, furan, pyrrole, indole, carbazole; the substitution comprises fluorine, chlorine, bromine, iodine, hydroxyl, carboxyl, sulfydryl, amino, primary amino, secondary amino, imino, nitro, cyano, alkyl, ester group, silicon group and acyl; r¹Including t-butyloxycarbonyl, isopropyloxycarbonyl, ethyloxycarbonyl and phenyl.

2. The method of claim 1, wherein the reaction steps are as follows:

(1) sequentially adding an iron compound x into the dried reaction tube₁mol% of additive x₂mol percent, fatty alcohol, azo compound and organic solvent, under argon atmosphere after the addition,stirring for dissolving, uniformly mixing, irradiating the reaction tube under light, continuously stirring and/or heating the reaction tube, wherein the addition amount of the fatty alcohol and the organic solvent is excessive;

(2) and (2) after the reaction in the step (1) is completed, removing the reaction tube from the light source, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an aminated product.

3. A process according to claim 1 or 2, wherein the iron compound is an iron-containing compound, including ferric or ferrous compounds; the ferric iron comprises ferric trichloride, ferric tribromide, ferric trifluoromethanesulfonate, ferric tetrafluoroborate, ferric hexafluorophosphate, ferric sulfate, ferric nitrate, ferric acetate, ferric trifluoroacetate, ferric citrate, ferric oxalate, ferric acrylate, tris (2,2,6, 6-tetramethyl-3, 5-heptanedionato) iron, ferric hydroxide, ferric acetylacetonate, ferric fluoride iron-containing compounds and hydrates thereof; the ferrous iron comprises ferrous chloride, ferrous bromide, ferrous iodide, ferrous trifluoromethanesulfonate, ferrous tetrafluoroborate, ferrous hexafluorophosphate, ferrous sulfate, ferrous nitrate, ferrous acetate, ferrous trifluoroacetate, ferrous citrate, ferrous oxalate, ferrous acrylate, ferrous bis (2,2,6, 6-tetramethyl-3, 5-heptanedionate), ferrous hydroxide, ferrous acetylacetonate, ferrous fluoride iron-containing compounds and hydrates thereof.

4. The method of claim 1 or 2, wherein the organic solvent is one or more of water, a hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogenated hydrocarbon solvent, a nitrohydrocarbon solvent, an ether solvent, a nitrile solvent, an ester solvent, an alcohol solvent, an amine solvent, an amide solvent, a sulfone solvent, and a sulfoxide solvent.

5. The method of claim 4, wherein the hydrocarbon solvent is one or more of benzene, toluene and saturated alkane compounds, the halogenated hydrocarbon solvent is one or more of trifluoromethylbenzene, chlorobenzene, dichloromethane, 1, 2-dichloroethane, chloroform and carbon tetrachloride, and the nitrohydrocarbon solvent is one or more of nitrobenzene and nitromethane; the ether solvent is one or more of tetrahydrofuran, 1, 4-dioxane, methyl tert-butyl ether and diethyl ether; the nitrile solvent is one or more of acetonitrile, benzonitrile and tert-butyl acetonitrile; the ester solvent is one or more of ethyl acetate, n-butyl acetate and isobutyl acetate; the alcohol solvent is one or more of methanol, ethanol, tert-butyl alcohol, n-butyl alcohol and cyclohexanol, and the amine solvent is one or more of triethylamine, diethylamine and diisopropylethylamine; the amide solvent is one or more of dimethylformamide and dimethylacetamide; the sulfoxide solvent is dimethyl sulfoxide, and can be used in any proportion in various cases.

6. The process of claim 4, wherein the organic solvent is acetonitrile, t-butyl acetonitrile, ethyl acetate, dichloromethane.

7. A process according to claim 1 or 2, wherein the additive comprises an alkali metal salt of a halide, an alkali metal salt of an organic acid compound, an alkali metal salt of a phenolic compound, an ammonium salt of a halide, an ammonium salt of an organic acid compound, an ammonium salt of a phenolic compound, wherein the halide is fluoride, chloride, bromide, iodide; the alkali metal salt is lithium salt, sodium salt, potassium salt or cesium salt; the organic acid compound is substituted or unsubstituted aryl carboxylic acid, substituted or unsubstituted alkyl carboxylic acid, substituted or unsubstituted aryl sulfonic acid, substituted or unsubstituted alkyl sulfonic acid, substituted or unsubstituted aryl phosphoric acid and substituted or unsubstituted alkyl phosphoric acid; the phenols are substituted or unsubstituted phenol compounds; the ammonium salt is tetramethylammonium salt, tetraethylammonium salt or tetrabutylammonium salt.

8. The process according to claim 1 or 2, wherein the additive is selected from the group consisting of sodium chloride, potassium chloride, tetrabutylammonium chloride, and potassium pentafluorophenol.

9. A process for the preparation of an iron-catalyzed 4-aminoalcohol according to claim 1 or 2, wherein the molar ratio of the iron compound to the fatty alcohol is less than 1; the heating condition temperature is as follows: placing the reacted system at 25-100 ℃; the illumination conditions include: the reacted system is exposed to visible light and/or monochromatic or mixed light of a wavelength of less than 500 nm.

10. A process for the preparation of an iron-catalyzed 4-aminoalcohol according to claim 9, wherein the molar ratio of iron compound to fatty alcohol is (0.01-0.1): 1; the illumination conditions are as follows: placing the reacted system under light with the wavelength of 350-450nm for irradiation; the iron compound is ferric chloride, ferric tribromide, ferric trifluoromethanesulfonate or ferric tetrafluoroborate.

Technical Field

The invention relates to the technical field of chemical synthesis, and particularly relates to a preparation method of iron-catalyzed 4-aminoalcohol.

Background

Amino alcohol is an important organic synthesis intermediate, and is widely applied to the fields of complex organic molecules, drug intermediates, life science, material science and the like. Selective carbon-hydrogen bond cleavage amination of fatty alcohols provides a favorable opportunity for studying molecular complexity and pharmaceutical intermediates, and makes it possible to construct nitrogen-containing compounds from inexpensive, readily available and abundant alcohols.

Remote carbon-hydrogen bond functionalization of alkanols can be achieved by the generation of oxygen radicals from fatty alcohols, followed by intramolecular 1, 5-hydrogen atom transfer. In the prior art, few reports are available for synthesizing the 4-aminoalcohol by directly using the cheap and easily obtained unprotected alcohol compounds as raw materials, mainly using silver, iridium, ruthenium, cerium and the like as metal catalysts, and the method is high in price and difficult in reaction operation and limits the synthesis development of preparing the 4-aminoalcohol compounds from alcohol.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a preparation method of iron-catalyzed 4-aminoalcohol, which directly performs carbon-hydrogen bond breaking and amination reaction selectively at the 4-position of 1,2 and 3-level fatty alcohol, namely, under the promotion of an iron catalyst and an additive and the irradiation of visible light, butanol, 4-aryl butanol and 4-alkyl butanol realize amination reaction through intramolecular free radical 1, 5-hydrogen migration to generate a series of 4-aminoalcohol compounds with different substituents.

In order to achieve the purpose, the technical scheme of the invention is as follows:

a method of preparing an iron-catalyzed 4-aminoalcohol, comprising the steps of: under the action of iron compound and under the condition of providing heating temperature and/or light energy, in the presence of azo compound and additive and in organic solvent to implement selective 4-hydrocarbon bond cleavage and amination of fatty alcohol so as to obtain 4-amino alcohol compound, its reaction formula is as follows:

the structural formula of the fatty alcohol is shown asAzo compoundsThe 4-aminoalcohol compound isWherein: r, R ', R' includes hydrogen, alkyl, substituted or unsubstituted phenyl, naphthyl, pyridine, thiophene, furan, pyrrole, indole, carbazole; the substitution comprises fluorine, chlorine, bromine, iodine, hydroxyl, carboxyl, sulfydryl, amino, primary amino, secondary amino, imino, nitro, cyano, alkyl, ester group, silicon group and acyl; r¹Including t-butyloxycarbonyl, isopropyloxycarbonyl, ethyloxycarbonyl and phenyl.

A preparation method of iron-catalyzed 4-aminoalcohol comprises the following reaction steps:

(1) sequentially adding an iron compound x1 mol%, an additive x2 mol%, fatty alcohol, an azo compound and an organic solvent into a dry reaction tube, stirring and dissolving the mixture in an argon atmosphere after the addition is finished, uniformly mixing the mixture, placing the reaction tube under light for irradiation and continuously stirring and/or heating the reaction tube, wherein the addition of the fatty alcohol and the organic solvent is excessive; the molar ratio of iron compound to additive is x 1: x2 ═ (0.1-10): 1;

(2) and (2) after the reaction in the step (1) is completed, removing the reaction tube from the light source, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an aminated product.

The iron compound is an iron-containing compound, including ferric iron or ferrous iron compounds; the ferric iron comprises ferric trichloride, ferric tribromide, ferric trifluoromethanesulfonate, ferric tetrafluoroborate, ferric hexafluorophosphate, ferric sulfate, ferric nitrate, ferric acetate, ferric trifluoroacetate, ferric citrate, ferric oxalate, ferric acrylate, tris (2,2,6, 6-tetramethyl-3, 5-heptanedionato) iron, ferric hydroxide, ferric acetylacetonate, ferric fluoride iron-containing compounds and hydrates thereof; the ferrous iron comprises ferrous chloride, ferrous bromide, ferrous iodide, ferrous trifluoromethanesulfonate, ferrous tetrafluoroborate, ferrous hexafluorophosphate, ferrous sulfate, ferrous nitrate, ferrous acetate, ferrous trifluoroacetate, ferrous citrate, ferrous oxalate, ferrous acrylate, ferrous bis (2,2,6, 6-tetramethyl-3, 5-heptanedionate), ferrous hydroxide, ferrous acetylacetonate, ferrous fluoride iron-containing compounds and hydrates thereof.

The organic solvent is one or more of water, hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, nitrohydrocarbon solvents, ether solvents, nitrile solvents, ester solvents, alcohol solvents, amine solvents, amide solvents, sulfone solvents and sulfoxide solvents.

The hydrocarbon solvent is one or more of benzene, toluene and saturated alkane compounds, the halogenated hydrocarbon solvent is one or more of trifluoromethylbenzene, chlorobenzene, dichloromethane, 1, 2-dichloroethane, chloroform and carbon tetrachloride, and the nitrohydrocarbon solvent is one or more of nitrobenzene and nitromethane; the ether solvent is one or more of tetrahydrofuran, 1, 4-dioxane, methyl tert-butyl ether and diethyl ether; the nitrile solvent is one or more of acetonitrile, benzonitrile and tert-butyl acetonitrile; the ester solvent is one or more of ethyl acetate, n-butyl acetate and isobutyl acetate; the alcohol solvent is one or more of methanol, ethanol, tert-butyl alcohol, n-butyl alcohol and cyclohexanol, and the amine solvent is one or more of triethylamine, diethylamine and diisopropylethylamine; the amide solvent is one or more of dimethylformamide and dimethylacetamide; the sulfoxide solvent is dimethyl sulfoxide, and can be used in any proportion in various cases.

Preferably, the solvent is acetonitrile, tert-butyl acetonitrile, ethyl acetate, dichloromethane.

The additive comprises alkali metal salts of halides, alkali metal salts of organic acid compounds, alkali metal salts of phenolic compounds, ammonium salts of halides, ammonium salts of organic acid compounds, ammonium salts of phenolic compounds, wherein the halides are fluorides, chlorides, bromides, iodides; the alkali metal salt is lithium salt, sodium salt, potassium salt or cesium salt; the organic acid compound is substituted or unsubstituted aryl carboxylic acid, substituted or unsubstituted alkyl carboxylic acid, substituted or unsubstituted aryl sulfonic acid, substituted or unsubstituted alkyl sulfonic acid, substituted or unsubstituted aryl phosphoric acid and substituted or unsubstituted alkyl phosphoric acid; the phenols are substituted or unsubstituted phenol compounds; the ammonium salt is tetramethylammonium salt, tetraethylammonium salt or tetrabutylammonium salt.

Preferably, the additive is sodium chloride, potassium chloride, tetrabutylammonium chloride and pentafluorophenol potassium salt.

The molar ratio of the iron compound to the azo compound is less than 1.

Preferably, the molar ratio of iron compound to azo compound is (0.01-0.1): 1.

preferably, the heating condition temperature is: the reacted system was placed at 25 ℃ to 100 ℃.

The illumination conditions include: the reacted system is exposed to visible light and/or monochromatic or mixed light of a wavelength of less than 500 nm.

Preferably, the system of the reaction is irradiated under light with a wavelength of 350-450 nm.

Preferably, the iron compound is ferric chloride, ferric tribromide, ferric trifluoromethanesulfonate, or ferric tetrafluoroborate.

The invention has the following beneficial effects:

the invention provides a convenient and rapid method for preparing various 4-amino alcohols, can directly use cheap and abundant fatty alcohol as a raw material, does not need to add promoters such as heavy metal salt, strong oxidant and the like, has great attraction on industrial production, simultaneously uses cheap metal for reaction, and has great application potential in the fields of metal catalysis, chemical synthesis and the like. The innovation points of the invention are as follows:

(1) the reaction only needs cheap and easily available iron catalyst.

(2) The reaction can be realized by using visible light as a light source and a blue LED lamp with the power of 1-200W.

(3) Fatty alcohol and azo compound which are widely available, cheap and easily available are used as substrates

(4) Short reaction time and high efficiency.

(5) The 4-aminoalcohol compounds with different substituents can be quickly and simply synthesized.

(6) The product is easy to separate and purify.

(7) And develops a cheap and easily-obtained methodology for selectively preparing the 4-aminoalcohol compound by 4-amination with the fatty alcohol through a one-step method, and the yield of the obtained corresponding 4-aminoalcohol compound is 26-92%.

(8) The method for providing selective amination of fatty alcohol can efficiently and quickly obtain a corresponding amination product under the catalysis of an iron compound and under the action of an additive under the condition of providing heat energy and/or light energy and/or microwaves; the reaction method has the advantages of mild conditions, neutral redox, short reaction time, safety, greenness, simple operation, no need of a large amount of high-valence metal salt, wide applicability of the substrate and great significance in industrial production.

Detailed Description

The concept and technical effects of the present invention will be clearly and completely described in the following embodiments to fully understand the objects, aspects and effects of the present invention.

Example 1

Adding ferric trichloride (0.004 mmol), tetrabutylammonium chloride (0.004 mmol), tert-butyloxycarbonyl substituted azo compound (0.4 mmol), benzene butanol (1.2 mmol) and anhydrous acetonitrile (4 ml) into a dried reaction tube in sequence, stirring and dissolving after the addition is finished, uniformly mixing, placing the reaction tube under light (hv) with the wavelength of 390nm for irradiation and continuous stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed liquid to a flask, carrying out reduced pressure distillation to obtain a crude product, carrying out rapid column chromatography to obtain an amination product of the benzene butanol of 127.0 mg, wherein the yield is 82%, and the product is a colorless oily substance. 1H NMR (400MHz, CDCl3) delta 7.46-7.18 (m,5H, Ar-H), 6.72-5.73 (m,1H, NH), 5.59-5.00 (m,1H, CH), 3.87-3.50 (m,2H, CH2),2.39(brs,1H, OH), 2.24-1.59 (m,4H, CH 2X 2), 1.59-0.95 (m,18H, X2). 13C NMR (101MHz, CDCl3) delta 156.0,155.1,139.7,128.4,127.9,127.6,81.4,81.1,62.2,59.2,29.6,28.2,27.4. Boc IR v (neat, cm-1)3447,2369,2063,1635,1508,1255,1167,1037. HRMS (ESI +) M/z Calcd for C21H34N2O6Na + [ M + Na ] + 433.2309; found 433.2317.

Example 2

The procedure is as described in example 1, except that the amounts of reagents used are: ferric chloride (0.008 mmol), tetrabutylammonium chloride (0.004 mmol), tert-butoxycarbonyl substituted azo compound (0.4 mmol), 4-methoxybenzenebutanol (208 μ l, 216.7 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under 390nm light (hv) for irradiation and heating to 60 ℃ for continuous stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of 4-methoxybenzyl butanol, wherein the amination product is 117.0 mg, and the yield is 71%. 1H NMR (400MHz, CDCl3) δ 7.34-7.14 (M,2H, Ar-H),6.83(d, J ═ 8.4Hz,2H, Ar-H), 6.59-5.62 (M,1H, NH), 5.60-4.94 (M,1H, CH),3.77(s,3H, CH3), 3.78-3.53 (M,2H, CH2), 2.33-1.77 (M,5H, OH + CH2 × 2), 1.64-0.96 (M, Boc × 2), 13C NMR (101MHz, CDCl3) δ 159.0,156.1,155.1,131.8,129.1,113.7,81.1,62.2,58.8,55.2,29.6,28.2,28.1,27.5.IR (neat, cm-1)3445, 76,2931, 1700.1, 294. v. (ESI, v.8, 55.2,29.6, 29.2, 29.1, 35, 35.5. C + hrn + cd 31 + (M, cd 31 +/M); found 437.1821.

Example 3

The procedure is as described in example 1, except that the amounts of reagents used are: iron tribromide (0.012 mmol), tetrabutylammonium chloride (0.004 mmol), tert-butoxycarbonyl substituted azo compound (0.4 mmol), 4-chlorobutanol (240.8 mg, 1.2 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under 390nm light (hv) for irradiation and heating to 80 ℃ for continuous stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of 4-chlorobutanol, wherein the amination product is 127.5 mg, and the yield is 76%. 1H NMR (400MHz, CDCl 3). delta.7.36-7.21 (m,4H, Ar-H), 6.91-5.74 (m,1H, NH), 5.76-4.99 (m,1H, CH), 3.79-3.55 (m,2H, CH2),2.46(brs,1H, OH), 2.22-0.99 (m,22H, Boc. times.2 + CH 2. times.2). 13C NMR (101MHz, CDCl 3). delta. 156.1,155.0,138.1,133.4,130.1,129.3,128.5,128.1,81.6,81.2,80.8,62.04,58.54,29.4,28.1,28.1,27.4,26.9.IR v (neat, cm-1)3443,2067,1641,1455,1365,1278,1261.HRMS (ESI +) M/z Calcd for C14H28N2O5Na + [ M + Na ] + 327.1890; found 327.1897.

Example 4

Iron tribromide (0.0008 mmol), tetrabutylammonium chloride (0.004 mmol), tert-butoxycarbonyl-substituted azo compound (0.4 mmol), butanol (110 μ l, 89.1 mg, 1.20 mmol), anhydrous acetonitrile (4 ml) were prepared as described in example 1; placing the reaction tube under light (hv) with the wavelength of 420nm for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, carrying out flash column chromatography to obtain an amination product of butanol, wherein the amination product is 92.0 mg, and the yield is 75%. 1H NMR (400MHz, CDCl3) δ 6.58-6.22 (M,1H, NH),3.63(t, J ═ 6.0Hz,2H, CH2),3.45(brs,2H, CH2),2.16(brs,1H, OH), 1.68-1.54 (M,4H, CH2 × 2), 1.51-1.35 (M,18H, Boc × 2), 13C NMR (101MHz, CDCl3) δ 155.4,81.1,62.26,50.3,49.1,29.6,28.2,23.8.IR v (neat, cm-1)3443,2067,1641,1455,1365,1278,1261.HRMS (ESI +) M/z: Calcd for C14H28N2O5 + 5Na + [ 56 + ] M +327.1890 +; found 327.1897.

Example 5

Iron tribromide (0.02 mmol), sodium chloride (0.004 mmol), tert-butoxycarbonyl-substituted azo compound (0.4 mmol), phenylpentanol (202 μ l, 197.0 mg, 1.20 mmol), anhydrous acetonitrile (4 ml) were prepared as described in example 1; placing the reaction tube under light (hv) with the wavelength of 380nm for irradiation, heating to 100 ℃, continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of the phenylpentanol, wherein the amination product is 95.1 mg, and the yield is 60%. 1H NMR (400MHz, CDCl3) delta 7.37-7.06 (M,5H, Ar-H), 6.50-5.40 (M,1H, NH), 4.77-4.15 (M,1H, CH), 3.79-3.43 (M,2H, CH2), 2.98-2.56 (M,2H, CH2),2.12(brs,1H, OH), 1.96-1.11 (M,22H, CH 2X 2+ Boc X2), 13C NMR (101MHz, CDCl3) delta 2, 81.3,80.9,62.2,60.1,57.3,39.2,29.4,28.1,28.0.IR (neat, cm-1) 43,2978,2933,2061, 1641, 3498, ESI 1,1390,1371, 35M [ 17H + CdZ ] 3+ [ 18H + 5H + (M H, 35 + Na +3 +; found 417.2368.

Example 6

The procedure is as described in example 1, except that the amounts of reagents used are: ferric triflate (0.024 mmol), sodium chloride (0.004 mmol), tert-butoxycarbonyl substituted azo compound (0.4 mmol), pentanol (130 μ l, 105.3 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under 390nm light (hv) for irradiation and heating to 60 ℃ for continuous stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an aminated product of pentanol, wherein the aminated product is 99.7 mg, and the yield is 78%. 1H NMR (400MHz, CDCl3) δ 6.46-5.97 (M,1H, NH), 4.38-3.95 (M,1H, CH), 3.73-3.47 (M,2H, CH2),2.32(brs,1H, OH), 1.79-1.23 (M,22H, Boc × 2+ CH2 × 2),1.08(d, J ═ 6.7Hz,3H, CH3), 13C NMR (101MHz, CDCl3) δ 2, 80.9,62.3,54.0,52.2,30.2,29.4,28.2,28.1,18.2.IR v (neat, cm-1)3451,3004,2367,2073,1637, 393, 1263,771,749.HRMS (ESI M/z: calc + Na 5 + [ 10 + Na ] +35 + 3+ (M +35 + 2 +); found 341.2054.

Example 7

The procedure is as described in example 1, except that the amounts of reagents used are: ferric triflate (0.028 mmol), sodium chloride (0.004 mmol), tert-butoxycarbonyl substituted azo compound (0.4 mmol), 1-hexanol (151 μ l, 122.9 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); the reaction tube was irradiated with light (hv) having a wavelength of 390nm while stirring, removed from the light source after the reaction was completed, the reaction mixture was transferred to a flask, and subjected to distillation under reduced pressure to obtain a crude product, which was subjected to flash column chromatography to obtain an aminated product of 1-hexanol, 117.4 mg, in a yield of 89%. 1H NMR (400MHz, CDCl3) delta 6.60-5.96 (M,1H, NH), 4.32-3.74 (M,1H, CH), 3.72-3.45 (M,2H, CH2),2.44(brs,1H, OH), 1.91-1.15 (M,24H, Boc x 2+ CH2 x 3), 1.02-0.71 (M,3H, CH3), 13C NMR (101MHz, CDCl3) delta 156.5,155.9,155.6,81.1,80.8,62.2,60.5,58.4,29.5,28.1,26.8,25.9,25.6,11.0.IR v (neat, cm-1)3441,2367,2349,2063,1637, 393, HRMS (ESI +) M/z: Cal 16H + Na 2+ 5 + Na 2O [ 3+ 35 +35 +; found 355.2211.

Example 8

As described in example 1, iron triflate (0.036 mmol), sodium chloride (0.004 mmol), tert-butoxycarbonyl substituted azo compound (0.4 mmol), cyclohexylethanol (167 μ l, 153.5 mg, 1.20 mmol), ethyl acetate (4 ml); placing the reaction tube under 390nm light (hv) for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of the cyclohexylethanol, wherein the amination product is 80.6 mg, and the yield is 56%. 1H NMR (400MHz, CDCl3) delta 6.96-6.03 (M,1H, NH), 3.87-3.42 (M,3H, CH2+ CH), 2.67-1.81 (M,3H, OH + CH2), 1.80-1.69 (M,1H, CH), 1.68-1.51 (M,3H, CH 2X 2.5), 1.49-1.36 (M,18H, Boc X2), 1.34-1.05 (M,4H, CH 2X 2), 1.04-0.77 (M,1H, hydrogen for one methylene). 13C NMR (101MHz, CDCl 48363), 80.9,80.5,60.3,59.9,35.9,35.4,35.0,32.0,31.4,29.6,28.2, 25.25 delta 4, V.9, 80.5,60.3,59.9,35.9,35.4,35.0,32.0,31.4,29.6,28.2, 25.25 V.9, 18H + CH 3879, Na + (M, 369, 31,27, 18, 3,17, 3, 9, 3; found 381.2368.

Example 9

The procedure is as described in example 1, except that the amounts of reagents used are: ferric triflate (0.032 mmol), pentafluorophenol potassium salt (0.004 mmol), tert-butyloxycarbonyl substituted azo compound (0.4 mmol), adamantane ethanol (218.7 mg, 0.4 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under 390nm light (hv) for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of the cyclohexylethanol, wherein the amination product is 103.7 mg, and the yield is 65%. 1H NMR (400MHz, CDCl3) delta 6.33-6.21 (M,1H, NH),4.22(M,1H, CH), 3.82-3.63 (M,2H, CH2), 2.29-1.32 (M,35H, hydrogen on ring + CH2+ OH + Boc X2). 13C NMR (101MHz, CDCl3) delta 155.8,155.6,81.5,81.0,80.8,61.5,58.4,43.9,42.2,39.4,37.7,37.6,36.3,32.9,31.3,28.5,28.2,28.1,27.9.IR v (neat, cm-1)3449,2986,2365, 1270, 1637, 2083, 1257, 751, HRMS (ESI M/z: Cal 22 + Na 2O +433.2673 + [ 29H 2+ ] C2 +; found 433.2685.

Example 10

Pentafluorophenol potassium salt additive (0.004 mmol) as in example 1, tert-butoxycarbonyl substituted azo compound (0.4 mmol), 4-methylpentanol (149. mu.l, 122.3 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under light (hv) with the wavelength of 390nm for irradiation, heating the reaction tube to 80 ℃, continuously stirring the reaction tube, removing the reaction tube from a light source after the reaction is finished, transferring a reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of 4-methylpentanol, wherein the amination product is 119.2 mg, and the yield is 86%. 1H NMR (400MHz, CDCl3) δ 6.47-6.34 (M,1H, NH),3.54(t, J ═ 6.5Hz,2H, CH2),2.46(brs,1H, OH), 1.99-1.84 (M,1H, hydrogen of one methylene), 1.70-1.60 (M,1H, hydrogen of one methylene), 1.59-1.31 (M,23H, Boc × 2+ CH2+ CH3), 1.27-1.14 (M,3H, CH3), 13C NMR (101MHz, CDCl3) δ 156.4,156.0,154.7,154.4,81.1,80.7,80.5,62.8,61.8,36.2,28.2,28.1,27.7,26.9,26.3.IR ν (neat, cm-1)3447,3008, 2065 + NH 5, 12517, 17 + N # 12, 17 + N # 12, 17 + (M, 17 + N # 12 + 17 + (M, 17 + N # 3+ N +; found 355.2212.

Example 11

As described in example 1, iron tetrafluoroborate (0.004 mmol), pentafluorophenol potassium salt (0.04 mmol), t-butoxycarbonyl substituted azo compound (0.4 mmol), 3-cyclopentylpropanol (156.9 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under the light (hv) with the wavelength of 390nm for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed liquid to a flask, carrying out reduced pressure distillation to obtain a crude product, carrying out flash column chromatography to obtain an amination product of 3-cyclopentyl propanol, wherein the amination product is 136.4 mg, and the yield is 92%. 1H NMR (400MHz, CDCl3) delta 6.49(s,1H, NH), 3.60-3.48 (M,2H, CH2),2.57(brs,1H, OH), 2.16-1.76 (M,4H, CH 2X 2), 1.75-1.46 (M,8H, CH 2X 4), 1.45-1.33 (M,18H, Boc X2). 13C NMR (101MHz, CDCl3) delta 2, 81.0,80.7,80.6,72.1,62.8,38.5,35.9,35.7,33.5,32.9,28.2,28.1,27.9,23.6,23.2,23.0,22.9.IR v (neat, cm-1)3353,2976,2363, ESI 3, 1615, 2063 + Na 2+ 743 + 18H + 18 +35 + HRZ 2; found381.2370.

Example 12

According to the method described in example 1, iron tetrafluoroborate (0.002 mmol), pentafluorophenol potassium salt (0.004 mmol), t-butoxycarbonyl substituted azo compound (0.4 mmol), 2-hexanol (151. mu.l, 122.9 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); the reaction tube was placed under light (hv) with a wavelength of 390nm and was continuously stirred, after the reaction was completed, the reaction tube was removed from the light source, the reaction mixture was transferred to a flask, and the crude product was obtained by distillation under reduced pressure, and flash column chromatography was carried out to obtain the aminated product of 2-hexanol in an amount of 103.3 mg with a yield of 74%. 1H NMR (400MHz, CDCl3) delta 6.82-6.04 (M,1H, NH), 4.33-3.92 (M,1H, CH), 3.85-3.58 (M,1H, CH),2.52(brs,1H, OH), 1.74-1.22 (M,22H, CH 2X 2+ Boc X2), 1.18-0.96 (M,6H, CH 3X 2).13C NMR (101MHz, CDCl3) delta 156.4,155.1,80.9,67.6,67.0,54.3,52.1,35.8,35.4,30.3,29.2,28.1,26.8,24.0,23.3,18.5,18.1.IR (neat, cm-1)3339,3320,2984, 37,1702, 1157, 1159, 29.11, 29.8, 24.0, 29.5, 29.1. V [ 17 ] NH 2+ Na + 46N 2+ (16 + NH 2 +; found 355.2211.

Example 13

According to the method described in example 1, iron tetrafluoroborate (0.0004 mmol), pentafluorophenol potassium salt (0.004 mmol), t-butoxycarbonyl substituted azo compound (0.4 mmol), ethyl 6-hydroxycaproate (191.2 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under light (hv) with the wavelength of 390nm for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an aminated product of 6-hydroxy ethyl caproate, wherein 124.2 mg of the aminated product is obtained, and the yield is 79%. 1H NMR (400MHz, CDCl3) delta 6.57-6.09 (M,1H, NH), 4.63-4.29 (M,1H, CH), 4.17-4.00 (M,2H, CH2), 3.75-3.46 (M,2H, CH2), 2.69-2.07 (M,3H, OH + CH2), delta 1.97-1.37 (M,22H, CH 2X 2+ Boc X2), 1.27-1.15 (M,3H, CH3).13C NMR (101MHz, CDCl3) delta 173.7,171.7,156.2,155.7,155.0,81.2,64.0,62.4,61.9,60.6,60.2,55.7,54.1,37.9,34.1,32.2,29.1,28.8,28.1,25.5, 25.24.5, 24.5, 24.6, 60.2,55.7,54.1,37.9,34.1,32.2,29.1,28.8, 28.5, 24.5 v.14, 27, 27.9, 27 + Na 3+ 27, 27-1, 18 + 27, 27H, 13H, 27H, 13C NMR, 27H, 13H, 27H, 13, 27, 35, 27, 35, 27, 35, 27, 35, 27.9, 27, 27.9, 27, 35, 27, 27.1, 27.8, III; found 413.2268.

Example 14

As described in example 1, ferric trichloride (0.0012 mmol), potassium chloride (0.004 mmol), tert-butoxycarbonyl-substituted azo compound (0.4 mmol), 6- ((tert-butyldimethylsilyl) oxy) hex-1-ol (293.3 mg, 1.30 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under light (hv) with the wavelength of 390nm for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring a reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of 6- ((tert-butyldimethylsilyl) oxy) hexan-1-ol, wherein the amination product is 112.4 mg, and the yield is 61%. 1H NMR (400MHz, CDCl3) delta 7.05-6.44 (M,1H, NH), 4.32-4.00 (M,1H, CH), 3.75-3.45 (M,4H, CH 2X 2),2.60(brs,1H, OH), 1.94-1.35 (M,24H, Boc X2 + CH 2X 3), 0.96-0.81 (M,9H, CH 3X 3), 0.09-0.06 (M,6H, CH 3X 2).13C NMR (101MHz, CDCl3) delta 155.7,80.7,80.4,62.8,62.5,62.0,61.4,60.8,55.9,35.6,35.2,32.6,29.4,28.7,28.2,28.1,25.9,25.7, 25.9,25.6, V # 3,2 # WO 3+ 5 + HRZ 2, 9,35.6,35.2, 2, 9, 35.6.6, 2, 9,2 # 19.6, 9,2 # 19.6, 9,2, 9, 9.6.6.6.6.6.6.6.6.6.6.6.6.7, 9, 9.8, 9, 9.6.6.6.8, 9, 9.6.6.8, 9, 9.8, 9.6.6.6.6.8, 9.8, 9, 9.6.6.6.6, 9, 9.6.6.6.8, 9, 9.6, 9, 9.6.6.6.6.6.6.6.9.9.9.9, 9, 9.6.6.9.9, 9, 9.6.6.6.6.6.6.6.6, 9, 9.9.9.9.9.9.9.9.9.9, 9, 9.9, 9, 9.9.9.9.9.9, 9.9.9, 9, 9.9.6.9.9.9.9.9.9.9.9.9.9.9.9.9.9.6, 9.9.9.6.6.6.6.6.6.8, 9.6.8, 9.9.9.; found 485.3022.

Example 15

As described in example 1, ferric trichloride (0.0016 mmol), potassium chloride (0.004 mmol), tert-butoxycarbonyl-substituted azo compound (0.4 mmol), 6-phenyloxyhex-1-ol (250.9 mg, 1.30 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under 390nm light (hv) for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of 6-phenyloxyhexyl-1-alcohol, wherein the amination product is 146.8 mg, and the yield is 85%. 1H NMR (400MHz, CDCl3) δ 7.20(t, J ═ 20.0Hz,2H, Ar-H), 6.99-6.67 (M,3H, Ar-H), 6.56-6.21 (M,1H, NH), 4.44-4.14 (M,2H, CH2), 4.11-3.77 (M,2H, CH2),1.96(brs,1H, OH), 1.83-1.56 (M,4H, CH2 × 2), 1.48-1.12 (M,18H Boc × 2), 13C NMR (101MHz, CDCl3) δ 158.7,158.2,156.2,155.6,129.3,120.9,120.5,114.3,80.9,66.4,65.0,62.0,55.9,32.3,32.0,29.4,28.8,28.5,28.2,28.0, 27.1249, 29.8, v ° 19.9, 18.8, 18H, C NMR (101MHz, cd 3) Δ 158.7,158.2,156.2,155.6,129.3,120.9,120.5,114.3,80.9, 18.9, 18, 18.8, 18 g, 18H, C, 2, 18H, 2, 18H, C, 2H, 18H, 2, 18H, 2H, 18H, 2H, 18H, 2H, 18H, 2H, 18H, 2H, 18H, 2H, 18H, 2H, 18H, 2H, 18H, 2H, 18H, 2H, ep H, 2H, ep H, 2, ep H, 2H, ep H, 2, ep H, 2, ep H, 2, ep H; found 447.2471.

Example 16

As described in example 1, iron trichloride (0.0032 mmol), potassium chloride (0.004 mmol), tert-butoxycarbonyl-substituted azo compound (0.4 mmol), 6- (naphthalen-1-yloxy) hex-1-ol (288.7 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under 390nm light (hv) for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of 6- (naphthalene-1-oxyl) hexan-1-ol, wherein the amination product is 124.9 mg, and the yield is 65%. 1H NMR (400MHz, CDCl3) delta 8.32-8.12 (M,1H, Ar-H), 7.88-7.73 (M,1H, Ar-H), 7.58-7.32 (M,4H, Ar-H), 6.87-6.74 (M,1H, Ar-H), 6.67-6.16 (M,1H, NH), 4.57-4.39 (M,1H, CH), 4.36-4.06 (M,2H, CH2), 3.86-3.49 (M,2H, CH2),2.22(brs,1H, OH), 2.12-1.58 (M,4H, CH 2X 2), 1.61-1.16 (M,18H, Boc X2), 13C NMR (101MHz, CDCl3) ESI 2, 81.4,80.9, 66.9, 66.32, 18, 18.9, 18, 9.32, 18, 9.8.32, 18, 9.8.8.9, 2,26,26,26,26,26,29 + (M,2,26,26,26,26,26,26,26,26,26,26,26,26,26,26,26,26,26,26,29 + (M) + [ 2,26,26,26,26,26,26,26,29 + (M,3,32 + (M,2,29 +); found 497.2623.

Example 17

As described in example 1, iron trichloride (0.0036 mmol), potassium chloride (0.004 mmol), tert-butoxycarbonyl-substituted azo compound (0.4 mmol), 6- (naphthalen-2-yloxy) hex-1-ol (293.5 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under 390nm light (hv) for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of 6- (naphthalene-2-yloxy) hexan-1-ol, wherein the amination product is 113.6 mg, and the yield is 60%. 1H NMR (400MHz, CDCl3) δ 7.82-7.64 (M,3H, Ar-H),7.41(t,1H J ═ 7.4Hz, Ar-H),7.31(t,1H J ═ 7.4Hz, Ar-H), 7.21-7.01 (M,2H, Ar-H), 6.84-6.43 (M,1H, NH), 4.60-3.98 (M,3H, CH + CH2), 3.81-3.46 (M,2H, CH2),2.61(brs,1H, OH), δ 2.21-1.56 (M,4H, CH2 × 2), 1.63-1.12 (M,18H, Boc × 2), 13C NMR (101MHz, CDCl 7) δ 156.7,156.1,155.7,134.4,129.2,128.8,127.5,126.7,126.2,123.4,118.9,118.5,106.8,106.3,81.3,80.9, 66.65, 62.65, 11.62, 11.9, 2 v.9, 2H, 29.9 + NH, 2,29 v.26, 29M, 29, 21 + NH, 2, 21 + 3.26, 21, 2, 29H, 13C NMR (M, 21, 11 cm, 11 cm, 9,2 cm, 9,11, 9,2, 9,2 cm, 9,2, 9,2, 9,2, 9,2, 9,2 cm, 2, 9,2, 9; found 497.2626.

Example 18

As described in example 1, ferric trichloride (0.0028 mmol), potassium chloride (0.004 mmol), tert-butoxycarbonyl-substituted azo compound (0.4 mmol), 6-hydroxyhexyl acetate (190.7 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under the light (hv) with the wavelength of 390nm for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed liquid to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of 6-hydroxyhexyl acetate, wherein the amination product is 120.4 mg, and the yield is 76%. 1H NMR (400MHz, CDCl3) delta 6.71-6.20 (M,1H, NH), 4.34-3.93 (M,3H, CH + CH2), 3.73-3.47 (M,2H, CH2),2.40(brs,1H, OH),2.01(s,3H, CH3), 1.90-1.27 (M,24H, CH 2X 3+ Boc X2), 13C NMR (101MHz, CDCl 5) delta 178.6,171.1,170.9,156.0,155.3,81.1,62.1,61.9,56.1,53.8,31.4,29.2,28.7,28.5,28.1,20.9.IR v (neat, cm-1)3455,2980,2941,2255,1706,1400, 3, 1253, 1369, ESIMS (740. ESI M.) + 8634H + 8678 [ CAZ ] Na + (18 + 8678 +/Na +35 +; found 413.2263.

Example 19

As described in example 1, iron tribromide (0.004 mmol), potassium chloride (0.004 mmol), tert-butoxycarbonyl-substituted azo compound (0.4 mmol), hexyl 6-hydroxybenzoate (276.9 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under 390nm light (hv) for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of the 6-hexyl hydroxybenzoate, wherein the amination product is 82.8 mg, and the yield is 45%. 1H NMR (400MHz, CDCl3) δ 8.02(d, J ═ 7.3Hz,2H, Ar-H),7.53(t, J ═ 7.4Hz,1H, Ar-H),7.41(t, J ═ 7.7Hz,2H, Ar-H),6.50(M,1H, NH), 4.58-4.15 (M,3H, CH + CH2), 3.79-3.53 (M,2H, CH2),2.38(brs,1H, OH), 2.08-1.56 (M,4H, CH2 × 2), 1.55-1.32 (M,18H, Boc × 2), 13C NMR (101MHz, CDCl3) δ 166.6,156.1,155.4,132.9,130.2,129.5,128.3,81.6,81.1,62.6,62.1,55.6,54.1, Boc × 2, 13C NMR (101MHz, CDCl3), δ 3876.6, 81.1,62.6,62.1, ESI, 19.0, Boc × 2, 19, v.6, 19 v. (101MHz, 35, 29, 35, 17 cm, 19M, 18H, 18 cm 2+ 19 cm 3H, 18 cm 2, 18 cm 3H, 18 cm 2, 18 cm 3H, 18 cm 3H, 18 cm 3H, 18 cm 3H, 18 cm 3H, 18 cm 3H, 18 cm 3M + (M +; found 475.2429.

Example 20

As described in example 1, iron tribromide (0.012 mmol), potassium chloride (0.004 mmol), tert-butoxycarbonyl-substituted azo compound (0.4 mmol), 6-carbazolylhexan-1-ol (339.0 mg, 1.30 mmol), ethyl acetate (4 ml); placing the reaction tube under 390nm light (hv) for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of 6-carbazolylhexan-1-ol, wherein the amination product is 84.4 mg, and the yield is 42%. 1H NMR (400MHz, CDCl3) δ 8.08(d, J ═ 7.6Hz,2H, Ar-H), 7.73-7.34 (M,4H, Ar-H), 7.25-7.11 (M,2H, Ar-H), 6.49-5.94 (M,1H, NH), 5.13-4.60 (M,1H, CH), 4.52-4.04 (M,2H, CH2), 3.74-3.43 (M,2H, CH2),2.07(brs,1H, OH), 1.77-1.36 (M,24H, CH2 × 3+ Boc × 2), 13C NMR (101MHz, CDCl3) δ 156.0,155.6,140.3,125.5,122.8,120.2,118.7,109.0,81.9,81.5,62.3,56.7,55.2,40.9,31.5,28.9, IR 19.28, v NMR (101MHz, CDCl3) δ 156.0,155.6,140.3,125.5,122.8,120.2,118.7,109.0,81.9, 62.3,56.7,55.2, 55.9, 31.5,28.9, ESI, 28.28.3, 1656H, 19, 19.3, 17 cm (M, 17 + hrm, 17M, 35, 17, 35, 17 cm 3,17 cm 3+ (M +; found 520.2798.

Example 21

As described in example 1, ferric chloride (0.0036 mmol), tetrabutylammonium chloride (0.004 mmol), tert-butoxycarbonyl-substituted azo compound (0.4 mmol), 6-indolyhex-1-ol (260.0 mg, 1.20 mmol), ethyl acetate (4 ml); placing the reaction tube under the light (hv) with the wavelength of 390nm for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of 6-indolylhexan-1-ol, wherein the amination product is 67.2 mg, and the yield is 40%. 1H NMR (400MHz, CDCl3) δ 7.56(d, J ═ 7.9Hz,1H, Ar-H),7.31(dd, J ═ 24.2,16.0Hz,1H, Ar-H), 7.25-7.06 (M,4H, Ar-H),6.44(M,1H, NH), 5.16-4.95 (M,2H, CH2), 4.88-4.21 (M,1H, CH),4.08(t, J ═ 7.0Hz,2H, CH2),3.58(t, J ═ 6.4Hz,2H, CH2),2.10(brs,1H, OH), 1.93-1.69 (M,2H, CH2), 1.61-1.43 (M,2H, CH2), 1.45-1.04 (br, v 1H, OH), 1.93-1.69 (M,2H, CH2), 1.61-1.43 (M, ESI, 21H, 21 cm, 12 cm, 3,8 cm, 3,8 cm, 3,8 cm, 3, 9 cm, 3, 9 cm, 3,8 cm, 9 cm, 3, 9 cm, 9 +3, 9 cm 3, 9 + 11 cm 3, 9 cm 3, 9 +3, 9,3, 9 cm 3, 9,3, 9 cm 3, 9 cm 3, 9 +3, 9 cm 3, 9 +3, 9 cm 3, 9 cm 3, 9 + 9 cm 3, 9 + 9,3, 9 + 9,9 cm 3, 9 + 9,9 +3, 9 cm 3, 9,3, 9 cm 3, 9 +3, 9 +3, 9 +3, 9,2 cm 3, 9; found 442.2324.

Example 22

As described in example 1, ferric trichloride (0.004 mmol), tetrabutylammonium chloride (0.036 mmol), isopropyloxycarbonyl-substituted azo compound (79 μ l, 81.1 mg, 0.40 mmol), phenylbutanol (183 μ l, 180.1 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under the light (hv) with the wavelength of 390nm for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed liquid to a flask, carrying out reduced pressure distillation to obtain a crude product, carrying out flash column chromatography to obtain an amination product of the isopropyl oxycarbonyl substituted azo compound and the phenylbutanol, wherein the amination product is 117.9 mg, and the yield is 84%. 1H NMR (400MHz, CDCl3) delta 7.42-7.13 (M,5H, Ar-H),5.91(M,1H, NH), 5.44-5.07 (M,1H, CH), 5.05-4.29 (M,2H, CH2), 3.75-3.36 (M,2H, CH2),2.43(brs,1H, OH), 2.24-1.44 (M,4H, CH 2X 2), 1.42-0.99 (M,12H, CH 3X 4), 13C NMR (101MHz, CDCl3) delta 156.6,155.7,139.2,128.4,127.9,127.7,70.2,69.6,62.1,59.8,29.4,26.6,21.9,21.8,21.7.IR v NMR (neat, cm-1) 51,2982,2367, 343,2053, 2058. IR v (Na + (10327 + 863) Na + (863 + 863) WO 27 + Na + (863 + 3627 + Na + (9, 17 + 868); found 375.1892.

Example 23

As described in example 1, ferric chloride (0.02 mmol), tetrabutylammonium chloride (0.04 mmol), ethyloxycarbonyl-substituted azo compound (63 μ l, 69.9 mg, 0.40 mmol), phenylbutanol (183 μ l, 180.1 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under the light (hv) with the wavelength of 390nm for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed liquid to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of the ethyl oxycarbonyl substituted azo compound and the benzene butanol, wherein the amination product is 88.9 mg, and the yield is 68%. 1H NMR (400MHz, CDCl3) delta 7.45-7.19 (M,5H, Ar-H), 6.81-5.88 (M,1H, NH), 5.49-5.05 (M,1H, CH), 4.51-3.94 (M,4H, CH 2X 2), 3.79-3.43 (M,2H, CH2), 2.69-1.48 (M,5H, OH + CH 2X 2), 1.42-0.62 (M,6H, CH 3X 2), 13C NMR (101MHz, CDCl3) delta 156.8,156.1,138.9,128.4,127.9,127.8,62.5,62.0,61.9,60.5,29.4,26.6, 14.3.IR v (neat, cm-1)3449,2990,2369,2082,1641,1508, ESI 2,1271, 1421 Na 8624 + Na + (751 + Na + 3624 + 8624 + O +/3627 +; found347.1587.

Example 24

As described in example 1, iron triflate (0.04 mmol), tetrabutylammonium chloride (0.008 mmol), benzyloxycarbonyl-substituted azo compound (129.1 mg, 0.43 mmol), phenylbutanol (183 μ l, 180.1 mg, 1.20 mmol), ethyl acetate (4 ml); placing the reaction tube under the light (hv) with the wavelength of 390nm for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed liquid to a flask, carrying out reduced pressure distillation to obtain a crude product, carrying out flash column chromatography to obtain an amination product of the benzyloxycarbonyl substituted azo compound and the benzene butanol, wherein the amination product is 51.4 mg, and the yield is 26%. 1H NMR (400MHz, CDCl3) delta 7.59-7.07 (M,15H, Ar-H), 6.96-5.99 (M,1H, NH), 5.55-4.95 (M,5H, CH + CH 2X 2), 3.84-3.32 (M,2H, CH2), 2.31-1.40 (M,5H, OH + CH 2X 2).13C NMR (101MHz, CDCl3) delta 156.6,155.9,138.7,135.7,135.4,128.5,128.3,128.1,127.9,68.2,67.7,62.2,60.5,29.5,26.6.IR v (neat, cm-1)3448,2367,2347,2069,1636,1524,1275,1260,763,750.HRMS (ESI +) M/z Calcd for C26H28N2O5Na [ M + Na ] + 471.1890; found 471.1900.

In conclusion, the method can use cheap and easily-obtained aliphatic alcohol or aromatic alcohol as a substrate to selectively aminate various organic compounds with different structures, and has the advantages of mild conditions, simple operation, short reaction time, greenness, high efficiency and wide application space.

The invention adopts the reaction condition of providing heat energy and/or light energy and/or microwaves, can realize the selective amination reaction of the fatty alcohol even under the condition of directly irradiating the blue LED lamp by one or more modes of simple heating, illumination or microwaves, does not need harsh reaction conditions such as high temperature, strong oxidant and the like or the addition of noble metal catalyst, has mild reaction conditions, is green and environment-friendly, is suitable for industrial production, and provides a new strategy for the diversity of chemical synthesis.