PREPARATION OF CHIRAL PRIMARY AMINE FROM ASYMMETRIC REDUCTIVE AMINATION OF SIMPLE KETONE CATALYZED BY RUTHENIUM-DIPHOSPHINE CATALYST

Abstract

The present invention relates to a preparation method of chiral primary amine. The chiral primary amine is prepared through a one-pot method that under the action of a ruthenium-chiral diphosphine catalyst, a simple ketone and an ammonium salt RCOONH.sub.4 have reductive amination by adding hydrogen and then are heated and hydrolyzed by adding acid. The present invention has the advantages of good substrate universality, high reaction efficiency and the like

##STR00001##

Claims

1. A preparation method of chiral primary amine, comprising: making a ketone compound and an ammonium salt, used as raw materials, react under the action of an organic solvent, hydrogen and a ruthenium-diphosphine catalyst to generate an intermediate, and performing acid adding and heating hydrolysis treatment on the intermediate to obtain the chiral primary amine.

2. The preparation method of the chiral primary amine according to claim 1, comprising: in an argon atmosphere, placing the ketone compound, the ammonium salt, the ruthenium-diphosphine catalyst and the organic solvent in a reaction flask, placing the reaction flask into an autoclave, injecting hydrogen for replacement in sequence, wherein a hydrogen pressure is 10 to 200 atm, performing oil-bath stirring treatment for 0.5 to 240 h under a temperature condition of 20° C. to 160° C., after cooling to a room temperature and releasing hydrogen, continuing to add protonic acid into the reaction flask and performing heating treatment for 0.5 to 240 h under a temperature condition of 20° C. to 160° C., and obtaining the chiral primary amine after neutralizing, washing, extracting and drying treatment.

3. The preparation method of the chiral primary amine according to claim 1, wherein the ketone compound is one of 4-methyl acetophenone, 3-methyl acetophenone, 4-tert-butyl acetophenone, 4-chloroacetophenone, 3-chloroacetophenone, 4-trifluoromethyl acetophenone, 3,4-dichloroacetophenone, 2-acetonaphthone, 1-propiophenone, 6,7,8,9-tetrahydro-5H-benzo[7]cyclopentane-5-one, 1-acetonaphthone and 3-acetylphenylethyl(methyl)carbamate.

4. The preparation method of the chiral primary amine according to claim 1, wherein the ammonium salt is an ammonium carboxylate salt.

5. The preparation method of the chiral primary amine according to claim 4, wherein a general formula of the ammonium carboxylate salt is R.sup.3COONH.sub.4, wherein R.sup.3 is one of alkyl, cycloalkyl, aryl, aralkyl, alkoxy, cycloalkoxy, aryloxy, aralkoxy and heterocyclyl.

6. The preparation method of the chiral primary amine according to claim 1, wherein a general formula of the ruthenium-diphosphine catalyst is RuX.sub.2L; wherein X is one of halogen anions, carboxylate anions, sulfooxy anions, a sulfate radical, a hydrogen sulfate radical, a dihydrogen phosphate radical, a monohydrogen phosphate radical, a phosphite radical, and a nitrate radical; and L is a chiral diphosphine ligand.

7. The preparation method of the chiral primary amine according to claim 1, wherein the organic solvent is one or several, of any proportion, of methanol, ethanol, isopropanol, butanol, tert-butanol, difluoroethanol, trifluoroethanol, hexafluoroisopropanol, tetrahydrofuran, toluene, dichloromethane and 1,2-dichloroethane.

8. The preparation method of the chiral primary amine according to claim 2, wherein protonic acid is one of hydrochloric acid, hydrobromic acid, sulfuric acid, methanesulfonic acid and p-toluenesulfonic acid.

9. The preparation method of the chiral primary amine according to claim 1, wherein in an argon atmosphere, 1 mmol and 134 mg of 4-methyl acetophenone, 0.5 mol % Ru(OAc).sub.2L.sub.5 ##STR00026## 2 mmol and 154 mg of NH.sub.4OAc and 2 mL of trifluoroethanol are added into a 5 mL ampoule, a reaction flask is placed in an autoclave, hydrogen is injected for replacement three times, 10 atm of hydrogen is injected each time, 50 atm of hydrogen is injected the last time, the autoclave is placed in an oil bath which is preheated in advance to a corresponding temperature, heating stirring is performed for 20 hours, cooling is performed to a room temperature, the hydrogen is slowly released, the reaction flask is taken out, 3 mL of a 6 M hydrogen chloride solution is added, heating is performed at 80° C. for 6 hours, cooling is performed, washing is performed with ethyl ether two times, a 4 M sodium hydroxide solution is used for neutralization till pH is 10, extraction is performed with ethyl ether three times, organic phases are combined, anhydrous sodium sulfate is used for drying, and vacuum drying is performed to obtain.

10. The preparation method of the chiral primary amine according to claim 1, wherein in an argon atmosphere, 1 mmol and 134 mg of 3-methyl acetophenone, 0.5 mol % Ru(OAc).sub.2L.sub.5 ##STR00027## 2 mmol and 154 mg of NH.sub.4OAc and 2 mL of trifluoroethanol are added into a 5 mL ampoule, a reaction flask is placed in an autoclave, hydrogen is injected for replacement three times, 10 atm of hydrogen is injected each time, 50 atm of hydrogen is injected the last time, the autoclave is placed in an oil bath which is preheated in advance to a corresponding temperature, heating stirring is performed for 20 hours, cooling is performed to a room temperature, the hydrogen is slowly released, the reaction flask is taken out, 3 mL of a 6 M hydrogen chloride solution is added, heating is performed at 80° C. for 6 hours, cooling is performed, washing is performed with ethyl ether two times, a 4 M sodium hydroxide solution is used for neutralization till pH is 10, extraction is performed with ethyl ether three times, organic phases are combined, anhydrous sodium sulfate is used for drying, and vacuum drying is performed to obtain.

11. The preparation method of the chiral primary amine according to claim 1, wherein in an argon atmosphere, 1 mmol and 176 mg of 4-tert-butyl acetophenone, 0.5 mol % Ru(OAc).sub.2L.sub.5 ##STR00028## 2 mmol and 154 mg of NH.sub.4OAc and 2 mL of trifluoroethanol are added into a 5 mL ampoule, a reaction flask is placed in an autoclave, hydrogen is injected for replacement three times, 10 atm of hydrogen is injected each time, 50 atm of hydrogen is injected the last time, the autoclave is placed in an oil bath which is preheated in advance to a corresponding temperature, heating stirring is performed for 20 hours, cooling is performed to a room temperature, the hydrogen is slowly released, the reaction flask is taken out, 3 mL of a 6 M hydrogen chloride solution is added, heating is performed at 80° C. for 6 hours, cooling is performed, washing is performed with ethyl ether two times, a 4 M sodium hydroxide solution is used for neutralization till pH is 10, extraction is performed with ethyl ether three times, organic phases are combined, anhydrous sodium sulfate is used for drying, and vacuum drying is performed to obtain.

12. The preparation method of the chiral primary amine according to claim 1, wherein in an argon atmosphere, 1 mmol and 154 mg of 4-chloroacetophenone, 0.5 mol % Ru(OAc).sub.2L.sub.5 ##STR00029## 2 mmol and 154 mg of NH.sub.4OAc and 2 mL of trifluoroethanol are added into a 5 mL ampoule, a reaction flask is placed in an autoclave, hydrogen is injected for replacement three times, 10 atm of hydrogen is injected each time, 50 atm of hydrogen is injected the last time, the autoclave is placed in an oil bath which is preheated in advance to a corresponding temperature, heating stirring is performed for 20 hours, cooling is performed to a room temperature, the hydrogen is slowly released, the reaction flask is taken out, 3 mL of a 6 M hydrogen chloride solution is added, heating is performed at 80° C. for 6 hours, cooling is performed, washing is performed with ethyl ether two times, a 4 M sodium hydroxide solution is used for neutralization till pH is 10, extraction is performed with ethyl ether three times, organic phases are combined, anhydrous sodium sulfate is used for drying, and vacuum drying is performed to obtain.

13. The preparation method of the chiral primary amine according to claim 1, wherein in an argon atmosphere, 1 mmol and 154 mg of 3-chloroacetophenone, 0.5 mol % Ru(OAc).sub.2L.sub.5 ##STR00030## 2 mmol and 154 mg of NH.sub.4OAc and 2 mL of trifluoroethanol are added into a 5 mL ampoule, a reaction flask is placed in an autoclave, hydrogen is injected for replacement three times, 10 atm of hydrogen is injected each time, 50 atm of hydrogen is injected the last time, the autoclave is placed in an oil bath which is preheated in advance to a corresponding temperature, heating stirring is performed for 20 hours, cooling is performed to a room temperature, the hydrogen is slowly released, the reaction flask is taken out, 3 mL of a 6 M hydrogen chloride solution is added, heating is performed at 80° C. for 6 hours, cooling is performed, washing is performed with ethyl ether two times, a 4 M sodium hydroxide solution is used for neutralization till pH is 10, extraction is performed with ethyl ether three times, organic phases are combined, anhydrous sodium sulfate is used for drying, and vacuum drying is performed to obtain.

14. The preparation method of the chiral primary amine according to claim 1, wherein in an argon atmosphere, 1 mmol and 188 mg of 4-trifluoromethyl acetophenone, 0.5 mol % Ru(OAc).sub.2L.sub.5 ##STR00031## 2 mmol and 154 mg of NH.sub.4OAc and 2 mL of trifluoroethanol are added into a 5 mL ampoule, a reaction flask is placed in an autoclave, hydrogen is injected for replacement three times, 10 atm of hydrogen is injected each time, 50 atm of hydrogen is injected the last time, the autoclave is placed in an oil bath which is preheated in advance to a corresponding temperature, heating stirring is performed for 20 hours, cooling is performed to a room temperature, the hydrogen is slowly released, the reaction flask is taken out, 3 mL of a 6 M hydrogen chloride solution is added, heating is performed at 80° C. for 6 hours, cooling is performed, washing is performed with ethyl ether two times, a 4 M sodium hydroxide solution is used for neutralization till pH is 10, extraction is performed with ethyl ether three times, organic phases are combined, anhydrous sodium sulfate is used for drying, and vacuum drying is performed to obtain.

15. The preparation method of the chiral primary amine according to claim 1, wherein in an argon atmosphere, 1 mmol and 189 mg of 3,4-dichloroacetophenone, 0.5 mol % Ru(OAc).sub.2L.sub.5 ##STR00032## 2 mmol and 154 mg of NH.sub.4OAc and 2 mL of trifluoroethanol are added into a 5 mL ampoule, a reaction flask is placed in an autoclave, hydrogen is injected for replacement three times, 10 atm of hydrogen is injected each time, 50 atm of hydrogen is injected the last time, the autoclave is placed in an oil bath which is preheated in advance to a corresponding temperature, heating stirring is performed for 20 hours, cooling is performed to a room temperature, the hydrogen is slowly released, the reaction flask is taken out, 3 mL of a 6 M hydrogen chloride solution is added, heating is performed at 80° C. for 6 hours, cooling is performed, washing is performed with ethyl ether two times, a 4 M sodium hydroxide solution is used for neutralization till pH is 10, extraction is performed with ethyl ether three times, organic phases are combined, anhydrous sodium sulfate is used for drying, and vacuum drying is performed to obtain.

16. The preparation method of the chiral primary amine according to claim 1, wherein in an argon atmosphere, 1 mmol and 170 mg of 2-acetonaphthone, 0.5 mol % Ru(OAc).sub.2L.sub.5 ##STR00033## 2 mmol and 154 mg of NH.sub.4OAc and 2 mL of trifluoroethanol are added into a 5 mL ampoule, a reaction flask is placed in an autoclave, hydrogen is injected for replacement three times, 10 atm of hydrogen is injected each time, 50 atm of hydrogen is injected the last time, the autoclave is placed in an oil bath which is preheated in advance to a corresponding temperature, heating stirring is performed for 20 hours, cooling is performed to a room temperature, the hydrogen is slowly released, the reaction flask is taken out, 3 mL of a 6 M hydrogen chloride solution is added, heating is performed at 80° C. for 6 hours, cooling is performed, washing is performed with ethyl ether two times, a 4 M sodium hydroxide solution is used for neutralization till pH is 10, extraction is performed with ethyl ether three times, organic phases are combined, anhydrous sodium sulfate is used for drying, and vacuum drying is performed to obtain.

17. The preparation method of the chiral primary amine according to claim 1, wherein in an argon atmosphere, 1 mmol and 134 mg of 1-propiophenone, 0.5 mol % Ru(OAc).sub.2L.sub.5 ##STR00034## 2 mmol and 154 mg of NH.sub.4OAc and 2 mL of trifluoroethanol are added into a 5 mL ampoule, a reaction flask is placed in an autoclave, hydrogen is injected for replacement three times, 10 atm of hydrogen is injected each time, 50 atm of hydrogen is injected the last time, the autoclave is placed in an oil bath which is preheated in advance to a corresponding temperature, heating stirring is performed for 20 hours, cooling is performed to a room temperature, the hydrogen is slowly released, the reaction flask is taken out, 3 mL of a 6 M hydrogen chloride solution is added, heating is performed at 80° C. for 6 hours, cooling is performed, washing is performed with ethyl ether two times, a 4 M sodium hydroxide solution is used for neutralization till pH is 10, extraction is performed with ethyl ether three times, organic phases are combined, anhydrous sodium sulfate is used for drying, and vacuum drying is performed to obtain.

18. The preparation method of the chiral primary amine according to claim 1, wherein in an argon atmosphere, 1 mmol and 160 mg of 6,7,8,9-tetrahydro-5H-benzo[7]cyclopentane-5-one, 0.5 mol % Ru(OAc).sub.2L.sub.1 ##STR00035## 2 mmol and 154 mg of NH.sub.4OAc and 2 mL of trifluoroethanol are added into a 5 mL ampoule, a reaction flask is placed in an autoclave, hydrogen is injected for replacement three times, 10 atm of hydrogen is injected each time, 50 atm of hydrogen is injected the last time, the autoclave is placed in an oil bath which is preheated in advance to a corresponding temperature, heating stirring is performed for 20 hours, cooling is performed to a room temperature, the hydrogen is slowly released, the reaction flask is taken out, 3 mL of a 6 M hydrogen chloride solution is added, heating is performed at 80° C. for 6 hours, cooling is performed, washing is performed with ethyl ether two times, a 4 M sodium hydroxide solution is used for neutralization till pH is 10, extraction is performed with ethyl ether three times, organic phases are combined, anhydrous sodium sulfate is used for drying, and vacuum drying is performed to obtain.

19. The preparation method of the chiral primary amine according to claim 1, wherein in an argon atmosphere, 5 mmol and 850 mg of 1-acetonaphthone, 0.1 mol % Ru(OAc).sub.2L.sub.1 ##STR00036## 2 mmol and 154 mg of NH.sub.4OAc and 2 mL of trifluoroethanol are added into a 5 mL ampoule, a reaction flask is placed in an autoclave, hydrogen is injected for replacement three times, 10 atm of hydrogen is injected each time, 50 atm of hydrogen is injected the last time, the autoclave is placed in an oil bath which is preheated in advance to a corresponding temperature, heating stirring is performed for 20 hours, cooling is performed to a room temperature, the hydrogen is slowly released, the reaction flask is taken out, 3 mL of a 6 M hydrogen chloride solution is added, heating is performed at 80° C. for 6 hours, cooling is performed, washing is performed with ethyl ether two times, a 4 M sodium hydroxide solution is used for neutralization till pH is 10, extraction is performed with ethyl ether three times, organic phases are combined, anhydrous sodium sulfate is used for drying, and vacuum drying is performed to obtain.

20. The preparation method of the chiral primary amine according to claim 1, wherein in an argon atmosphere, 1 mmol and 221 mg of 3-acetylphenylethyl(methyl)carbamate, 0.2 mol % Ru(OAc).sub.2L.sub.1 ##STR00037## 2 mmol and 154 mg of NH.sub.4OAc and 2 mL of trifluoroethanol are added into a 5 mL ampoule, a reaction flask is placed in an autoclave, hydrogen is injected for replacement three times, 10 atm of hydrogen is injected each time, 50 atm of hydrogen is injected the last time, the autoclave is placed in an oil bath which is preheated in advance to a corresponding temperature, heating stirring is performed for 20 hours, cooling is performed to a room temperature, the hydrogen is slowly released, the reaction flask is taken out, 3 mL of a 6 M hydrogen chloride solution is added, heating is performed at 80° C. for 6 hours, cooling is performed, washing is performed with ethyl ether two times, a 4 M sodium hydroxide solution is used for neutralization till pH is 10, extraction is performed with ethyl ether three times, organic phases are combined, anhydrous sodium sulfate is used for drying, and vacuum drying is performed to obtain.

Description

DETAILED DESCRIPTION OF THE PRESENT INVENTION

[0050] The present invention is described below through embodiments, but the present invention is not limited to the embodiments.

Embodiment 1

[0051] In an argon atmosphere, acetophenone (1 mmol, 120 mg), RuX.sub.2L and NH.sub.4X (2 mmol) were added into a 5 mL ampoule. A corresponding solvent (2 mL) was added, and a reaction flask was placed in an autoclave. Hydrogen was injected for replacement three times, wherein 10 atm of hydrogen was injected each time, and hydrogen of required pressure was injected the last time. The autoclave was placed in an oil bath which was preheated in advance to a corresponding temperature, and heating stirring was performed for 24 hours. Cooling was performed to a room temperature. The hydrogen was slowly released, and the reaction flask was taken out. 3 mL of a 6 M hydrogen chloride solution was added, and heating was performed at 80° C. for 6 hours. Cooling was performed, and washing was performed with ethyl ether two times. A 4 M sodium hydroxide solution was used for neutralization till pH was 10. Extraction was performed with ethyl ether three times, and organic phases were combined. Anhydrous sodium sulfate was used for drying, and vacuum drying was performed to obtain pure 1-phenylethylamine. For measurement of enantioselectivity of a product, the product needs to be acetylated first, and corresponding yields and enantioselectivity are as shown in Table 1.

TABLE-US-00001 TABLE 1 Preparation of Chiral 1-phenylethylamine through Asymmetric Reductive Amination of Acetophenone [00007] [00008] Entry NH.sub.4X RuX.sub.2L (x mol %) H.sub.2 (atm) Temp. (° C) Solvent Yield (%) Ee (%) 1 NH.sub.4OAc Ru(OAc).sub.2L.sub.1 (1) 50 80 MeOH 58 33 2 NH.sub.4OAc Ru(OAc).sub.2L.sub.1 (1) 50 80 EtOH 46 48 3 NH.sub.4OAc Ru(OAc).sub.2L.sub.1 (1) 50 80 .sup.iPrOH 35 59 4 NH.sub.4OAc Ru(OAc).sub.2L.sub.1 (1) 50 80 THF 18 57 5 NH.sub.4OAc Ru(OAc).sub.2L.sub.1 (1) 50 80 TFE 96 75 6 PhCOONH.sub.4 Ru(OAc).sub.2L.sub.1 (1) 50 80 TFE 96 70 7 NH.sub.4OAc RuCl.sub.2L.sub.1 (1) 50 80 TFE 91 78 8 NH.sub.4OAc RuCl.sub.2L.sub.2 (1) 50 80 TFE 90 74 9 NH.sub.4OAc RuCl.sub.2L.sub.3 (1) 50 80 TFE 89 76 10 NH.sub.4OAc RuCl.sub.2L.sub.4 (1) 50 80 TFE 93 89 11 NH.sub.4OAc RuCl.sub.2L.sub.5 (1) 50 80 TFE 94 94 12 NH.sub.4OAc Ru(OAc).sub.2L.sub.5 (1) 50 80 TFE 92 97 13 NH.sub.4OAc Ru(OAc).sub.2L.sub.5 (1) 70 80 TFE 98 96 14 NH.sub.4OAc Ru(OAc).sub.2L.sub.5 (0.5) 50 100 TFE 98 96 15 NH.sub.4OAc Ru(OAc).sub.2L.sub.6 (1) 50 80 TFE 92 65 16 NH.sub.4OAc Ru(OAc).sub.2L.sub.7 (1) 50 80 TFE 92 67 17 NH.sub.4OAc Ru(OAc).sub.2L.sub.5 (0.1) 60 120 TFE 80 94 18 NH.sub.4OAc Ru(OAc).sub.2L.sub.1 (0.1) 60 120 TFE 96 82 19 NH.sub.4OAc Ru(OAc).sub.2L.sub.1 (0.01) 60 120 TFE 38 82

##STR00009##

[0052] Compared with Entry 18 in embodiment 1, a 6 M hydrochloric acid solution was not added for heating treatment in post-treatment.

[0053] In an argon atmosphere, acetophenone (1 mmol, 120 mg), Ru(OAc).sub.2L.sub.1 (0.1 mol %), NH.sub.4OAc (2 mmol, 154 mg) and trifluoroethanol (2 mL) were added into a 5 mL ampoule. A reaction flask was placed in an autoclave. Hydrogen was injected for replacement three times, wherein 10 atm of hydrogen was injected each time, and 50 atm of hydrogen was injected the last time. The autoclave was placed in an oil bath which was preheated in advance to a corresponding temperature, and stirring was performed for 24 hours while heating was performed to 120° C. Cooling was performed to a room temperature. The hydrogen was slowly released, and the reaction flask was taken out. Cooling was performed, and washing was performed with ethyl ether two times. A 4 M sodium hydroxide solution was used for neutralization till pH was 10. Extraction was performed with ethyl ether three times, and organic phases were combined. Anhydrous sodium sulfate was used for drying, and vacuum drying was performed to obtain 97 mg of pure (S)-1-(phenyl)ethane-1-amine with 81% yield and 82% ee.

##STR00010##

[0054] In an argon atmosphere, 4-methyl acetophenone (1 mmol, 134 mg), Ru(OAc).sub.2L.sub.5 (0.5 mol %), NH.sub.4OAc (2 mmol, 154 mg) and trifluoroethanol (2 mL) were added into a 5 mL ampoule. A reaction flask was placed in an autoclave. Hydrogen was injected for replacement three times, wherein 10 atm of hydrogen was injected each time, and 50 atm of hydrogen was injected the last time. The autoclave was placed in an oil bath which was preheated in advance to a corresponding temperature, and heating stirring was performed for 20 hours. Cooling was performed to a room temperature. The hydrogen was slowly released, and the reaction flask was taken out. 3 mL of a 6 M hydrogen chloride solution was added, and heating was performed at 80° C. for 6 hours. Cooling was performed, and washing was performed with ethyl ether two times. A 4 M sodium hydroxide solution was used for neutralization till pH was 10. Extraction was performed with ethyl ether three times, and organic phases were combined. Anhydrous sodium sulfate was used for drying, and vacuum drying was performed to obtain 117 mg of pure (R)-1-(p-methylphenyl)ethane-1-amine with 87% yield and 96% ee.

##STR00011##

[0055] In an argon atmosphere, 3-methyl acetophenone (1 mmol, 134 mg), Ru(OAc).sub.2L.sub.5 (0.5 mol %), NH.sub.4OAc (2 mmol, 154 mg) and trifluoroethanol (2 mL) were added into a 5 mL ampoule. A reaction flask was placed in an autoclave. Hydrogen was injected for replacement three times, wherein 10 atm of hydrogen was injected each time, and 50 atm of hydrogen was injected the last time. The autoclave was placed in an oil bath which was preheated in advance to a corresponding temperature, and heating stirring was performed for 20 hours. Cooling was performed to a room temperature. The hydrogen was slowly released, and the reaction flask was taken out. 3 mL of a 6 M hydrogen chloride solution was added, and heating was performed at 80° C. for 6 hours. Cooling was performed, and washing was performed with ethyl ether two times. A 4 M sodium hydroxide solution was used for neutralization till pH was 10. Extraction was performed with ethyl ether three times, and organic phases were combined. Anhydrous sodium sulfate was used for drying, and vacuum drying was performed to obtain 120 mg of pure (R)-1-(m-methylphenyl)ethane-1-amine with 89% yield and 91% ee.

##STR00012##

[0056] In an argon atmosphere, 4-tert-butyl acetophenone (1 mmol, 176 mg), Ru(OAc).sub.2L.sub.5 (0.5 mol %), NH.sub.4OAc (2 mmol, 154 mg) and trifluoroethanol (2 mL) were added into a 5 mL ampoule. A reaction flask was placed in an autoclave. Hydrogen was injected for replacement three times, wherein 10 atm of hydrogen was injected each time, and 50 atm of hydrogen was injected the last time. The autoclave was placed in an oil bath which was preheated in advance to a corresponding temperature, and heating stirring was performed for 20 hours. Cooling was performed to a room temperature. The hydrogen was slowly released, and the reaction flask was taken out. 3 mL of a 6 M hydrogen chloride solution was added, and heating was performed at 80° C. for 6 hours. Cooling was performed, and washing was performed with ethyl ether two times. A 4 M sodium hydroxide solution was used for neutralization till pH was 10. Extraction was performed with ethyl ether three times, and organic phases were combined. Anhydrous sodium sulfate was used for drying, and vacuum drying was performed to obtain 134 mg of pure (R)-1-(4-(tert-butyl)phenyl)ethane-1-amine with 76% yield and 87% ee.

##STR00013##

[0057] In an argon atmosphere, 4-methoxy acetophenone (1 mmol, 150 mg), Ru(OAc).sub.2L.sub.5 (0.5 mol %), NH.sub.4OAc (2 mmol, 154 mg) and trifluoroethanol (2 mL) were added into a 5 mL ampoule. A reaction flask was placed in an autoclave. Hydrogen was injected for replacement three times, wherein 10 atm of hydrogen was injected each time, and 50 atm of hydrogen was injected the last time. The autoclave was placed in an oil bath which was preheated in advance to a corresponding temperature, and heating stirring was performed for 20 hours. Cooling was performed to a room temperature. The hydrogen was slowly released, and the reaction flask was taken out. 3 mL of a 6 M hydrogen chloride solution was added, and heating was performed at 80° C. for 6 hours. Cooling was performed, and washing was performed with ethyl ether two times. A 4 M sodium hydroxide solution was used for neutralization till pH was 10. Extraction was performed with ethyl ether three times, and organic phases were combined. Anhydrous sodium sulfate was used for drying, and vacuum drying was performed to obtain 143.5 mg of pure (R)-1-(4-methoxyphenyl)ethane-1-amine with 95% yield and 89% ee.

##STR00014##

[0058] In an argon atmosphere, 3-methoxy acetophenone (1 mmol, 150 mg), Ru(OAc).sub.2L.sub.5 (0.2 mol %), NH.sub.4OAc (2 mmol, 154 mg) and trifluoroethanol (2 mL) were added into a 5 mL ampoule. A reaction flask was placed in an autoclave. Hydrogen was injected for replacement three times, wherein 10 atm of hydrogen was injected each time, and 50 atm of hydrogen was injected the last time. The autoclave was placed in an oil bath which was preheated in advance to a corresponding temperature, and heating stirring was performed for 20 hours. Cooling was performed to a room temperature. The hydrogen was slowly released, and the reaction flask was taken out. 3 mL of a 6 M hydrogen chloride solution was added, and heating was performed at 80° C. for 6 hours. Cooling was performed, and washing was performed with ethyl ether two times. A 4 M sodium hydroxide solution was used for neutralization till pH was 10. Extraction was performed with ethyl ether three times, and organic phases were combined. Anhydrous sodium sulfate was used for drying, and vacuum drying was performed to obtain 138 mg of pure (R)-1-(3-methoxyphenyl)ethane-1-amine with 91% yield and 94% ee.

##STR00015##

[0059] In an argon atmosphere, 4-fluoroacetophenone (1 mmol, 138 mg), Ru(OAc).sub.2L.sub.5 (0.2 mol %), NH.sub.4OAc (2 mmol, 154 mg) and trifluoroethanol (2 mL) were added into a 5 mL ampoule. A reaction flask was placed in an autoclave. Hydrogen was injected for replacement three times, wherein 10 atm of hydrogen was injected each time, and 50 atm of hydrogen was injected the last time. The autoclave was placed in an oil bath which was preheated in advance to a corresponding temperature, and heating stirring was performed for 20 hours. Cooling was performed to a room temperature. The hydrogen was slowly released, and the reaction flask was taken out. 3 mL of a 6 M hydrogen chloride solution was added, and heating was performed at 80° C. for 6 hours. Cooling was performed, and washing was performed with ethyl ether two times. A 4 M sodium hydroxide solution was used for neutralization till pH was 10. Extraction was performed with ethyl ether three times, and organic phases were combined. Anhydrous sodium sulfate was used for drying, and vacuum drying was performed to obtain 127 mg of pure (R)-1-(4-fluorophenyl)ethane-1-amine with 91% yield and 95% ee.

##STR00016##

[0060] In an argon atmosphere, 3-fluoroacetophenone (1 mmol, 138 mg), Ru(OAc).sub.2L.sub.5 (0.2 mol %), NH.sub.4OAc (2 mmol, 154 mg) and trifluoroethanol (2 mL) were added into a 5 mL ampoule. A reaction flask was placed in an autoclave. Hydrogen was injected for replacement three times, wherein 10 atm of hydrogen was injected each time, and 50 atm of hydrogen was injected the last time. The autoclave was placed in an oil bath which was preheated in advance to a corresponding temperature, and heating stirring was performed for 20 hours. Cooling was performed to a room temperature. The hydrogen was slowly released, and the reaction flask was taken out. 3 mL of a 6 M hydrogen chloride solution was added, and heating was performed at 80° C. for 6 hours. Cooling was performed, and washing was performed with ethyl ether two times. A 4 M sodium hydroxide solution was used for neutralization till pH was 10. Extraction was performed with ethyl ether three times, and organic phases were combined. Anhydrous sodium sulfate was used for drying, and vacuum drying was performed to obtain 127 mg of pure (R)-1-(3-fluorophenyl)ethane-1-amine with 91% yield and 95% ee.

##STR00017##

[0061] In an argon atmosphere, 4-chloroacetophenone (1 mmol, 154 mg), Ru(OAc).sub.2L.sub.5 (0.5 mol %), NH.sub.4OAc (2 mmol, 154 mg) and trifluoroethanol (2 mL) were added into a 5 mL ampoule. A reaction flask was placed in an autoclave. Hydrogen was injected for replacement three times, wherein 10 atm of hydrogen was injected each time, and 50 atm of hydrogen was injected the last time. The autoclave was placed in an oil bath which was preheated in advance to a corresponding temperature, and heating stirring was performed for 20 hours. Cooling was performed to a room temperature. The hydrogen was slowly released, and the reaction flask was taken out. 3 mL of a 6 M hydrogen chloride solution was added, and heating was performed at 80° C. for 6 hours. Cooling was performed, and washing was performed with ethyl ether two times. A 4 M sodium hydroxide solution was used for neutralization till pH was 10. Extraction was performed with ethyl ether three times, and organic phases were combined. Anhydrous sodium sulfate was used for drying, and vacuum drying was performed to obtain 120 mg of pure (R)-1-(4-chlorophenyl)ethane-1-amine with 77% yield and 96% ee.

##STR00018##

[0062] In an argon atmosphere, 3-chloroacetophenone (1 mmol, 154 mg), Ru(OAc).sub.2L.sub.5 (0.5 mol %), NH.sub.4OAc (2 mmol, 154 mg) and trifluoroethanol (2 mL) were added into a 5 mL ampoule. A reaction flask was placed in an autoclave. Hydrogen was injected for replacement three times, wherein 10 atm of hydrogen was injected each time, and 50 atm of hydrogen was injected the last time. The autoclave was placed in an oil bath which was preheated in advance to a corresponding temperature, and heating stirring was performed for 20 hours. Cooling was performed to a room temperature. The hydrogen was slowly released, and the reaction flask was taken out. 3 mL of a 6 M hydrogen chloride solution was added, and heating was performed at 80° C. for 6 hours. Cooling was performed, and washing was performed with ethyl ether two times. A 4 M sodium hydroxide solution was used for neutralization till pH was 10. Extraction was performed with ethyl ether three times, and organic phases were combined. Anhydrous sodium sulfate was used for drying, and vacuum drying was performed to obtain 121 mg of pure (R)-1-(3-chlorophenyl)ethane-1-amine with 81% yield and 94% ee.

##STR00019##

[0063] In an argon atmosphere, 4-trifluoromethyl acetophenone (1 mmol, 188 mg), Ru(OAc).sub.2L.sub.5 (0.5 mol %), NH.sub.4OAc (2 mmol, 154 mg) and trifluoroethanol (2 mL) were added into a 5 mL ampoule. A reaction flask was placed in an autoclave. Hydrogen was injected for replacement three times, wherein 10 atm of hydrogen was injected each time, and 50 atm of hydrogen was injected the last time. The autoclave was placed in an oil bath which was preheated in advance to a corresponding temperature, and heating stirring was performed for 20 hours. Cooling was performed to a room temperature. The hydrogen was slowly released, and the reaction flask was taken out. 3 mL of a 6 M hydrogen chloride solution was added, and heating was performed at 80° C. for 6 hours. Cooling was performed, and washing was performed with ethyl ether two times. A 4 M sodium hydroxide solution was used for neutralization till pH was 10. Extraction was performed with ethyl ether three times, and organic phases were combined. Anhydrous sodium sulfate was used for drying, and vacuum drying was performed to obtain 198 mg of pure (R)-1-(4-(trifluoromethyl)phenyl)ethane-1-amine with 75% yield and 96% ee.

##STR00020##

[0064] In an argon atmosphere, 3,4-dichloroacetophenone (1 mmol, 189 mg), Ru(OAc).sub.2L.sub.5 (0.5 mol %), NH.sub.4OAc (2 mmol, 154 mg) and trifluoroethanol (2 mL) were added into a 5 mL ampoule. A reaction flask was placed in an autoclave. Hydrogen was injected for replacement three times, wherein 10 atm of hydrogen was injected each time, and 50 atm of hydrogen was injected the last time. The autoclave was placed in an oil bath which was preheated in advance to a corresponding temperature, and heating stirring was performed for 20 hours. Cooling was performed to a room temperature. The hydrogen was slowly released, and the reaction flask was taken out. 3 mL of a 6 M hydrogen chloride solution was added, and heating was performed at 80° C. for 6 hours. Cooling was performed, and washing was performed with ethyl ether two times. A 4 M sodium hydroxide solution was used for neutralization till pH was 10. Extraction was performed with ethyl ether three times, and organic phases were combined. Anhydrous sodium sulfate was used for drying, and vacuum drying was performed to obtain 115 mg of pure (R)-1-(3,4-dichlorophenyl)ethane-1-amine with 89% yield and 90% ee.

##STR00021##

[0065] In an argon atmosphere, 2-acetonaphthone (1 mmol, 170 mg), Ru(OAc).sub.2L.sub.5 (0.5 mol %), NH.sub.4OAc (2 mmol, 154 mg) and trifluoroethanol (2 mL) were added into a 5 mL ampoule. A reaction flask was placed in an autoclave. Hydrogen was injected for replacement three times, wherein 10 atm of hydrogen was injected each time, and 50 atm of hydrogen was injected the last time. The autoclave was placed in an oil bath which was preheated in advance to a corresponding temperature, and heating stirring was performed for 20 hours. Cooling was performed to a room temperature. The hydrogen was slowly released, and the reaction flask was taken out. 3 mL of a 6 M hydrogen chloride solution was added, and heating was performed at 80° C. for 6 hours. Cooling was performed, and washing was performed with ethyl ether two times. A 4 M sodium hydroxide solution was used for neutralization till pH was 10. Extraction was performed with ethyl ether three times, and organic phases were combined. Anhydrous sodium sulfate was used for drying, and vacuum drying was performed to obtain 148 mg of pure (R)-1-(naphthalen-2-yl)ethane-1-amine with 89% yield and 94% ee.

##STR00022##

[0066] In an argon atmosphere, 1-propiophenone (1 mmol, 134 mg), Ru(OAc).sub.2L.sub.5 (0.5 mol %), NH.sub.4OAc (2 mmol, 154 mg) and trifluoroethanol (2 mL) were added into a 5 mL ampoule. A reaction flask was placed in an autoclave. Hydrogen was injected for replacement three times, wherein 10 atm of hydrogen was injected each time, and 50 atm of hydrogen was injected the last time. The autoclave was placed in an oil bath which was preheated in advance to a corresponding temperature, and heating stirring was performed for 20 hours. Cooling was performed to a room temperature. The hydrogen was slowly released, and the reaction flask was taken out. 3 mL of a 6 M hydrogen chloride solution was added, and heating was performed at 80° C. for 6 hours. Cooling was performed, and washing was performed with ethyl ether two times. A 4 M sodium hydroxide solution was used for neutralization till pH was 10. Extraction was performed with ethyl ether three times, and organic phases were combined. Anhydrous sodium sulfate was used for drying, and vacuum drying was performed to obtain 109 mg of pure (R)-1-phenylpropane-1-amine with 84% yield and 97% ee.

##STR00023##

[0067] In an argon atmosphere, 6,7,8,9-tetrahydro-5H-benzo[7]cyclopentane-5-one (1 mmol, 160 mg), Ru(OAc).sub.2L.sub.1 (0.5 mol %), NH.sub.4OAc (2 mmol, 154 mg) and trifluoroethanol (2 mL) were added into a 5 mL ampoule. A reaction flask was placed in an autoclave. Hydrogen was injected for replacement three times, wherein 10 atm of hydrogen was injected each time, and 50 atm of hydrogen was injected the last time. The autoclave was placed in an oil bath which was preheated in advance to a corresponding temperature, and heating stirring was performed for 20 hours. Cooling was performed to a room temperature. The hydrogen was slowly released, and the reaction flask was taken out. 3 mL of a 6 M hydrogen chloride solution was added, and heating was performed at 80° C. for 6 hours. Cooling was performed, and washing was performed with ethyl ether two times. A 4 M sodium hydroxide solution was used for neutralization till pH was 10. Extraction was performed with ethyl ether three times, and organic phases were combined. Anhydrous sodium sulfate was used for drying, and vacuum drying was performed to obtain pure (R)-6,7,8,9-tetrahydro-5H-benzo[7]cyclopentane-5-amine with 91% yield and 84% ee.

##STR00024##

[0068] In an argon atmosphere, 1-acetonaphthone (5 mmol, 850 mg), Ru(OAc).sub.2L.sub.1 (0.1 mol %), NH.sub.4OAc (2 mmol, 154 mg) and trifluoroethanol (2 mL) were added into a 5 mL ampoule. A reaction flask was placed in an autoclave. Hydrogen was injected for replacement three times, wherein 10 atm of hydrogen was injected each time, and 50 atm of hydrogen was injected the last time. The autoclave was placed in an oil bath which was preheated in advance to a corresponding temperature, and heating stirring was performed for 20 hours. Cooling was performed to a room temperature. The hydrogen was slowly released, and the reaction flask was taken out. 3 mL of a 6 M hydrogen chloride solution was added, and heating was performed at 80° C. for 6 hours. Cooling was performed, and washing was performed with ethyl ether two times. A 4 M sodium hydroxide solution was used for neutralization till pH was 10. Extraction was performed with ethyl ether three times, and organic phases were combined. Anhydrous sodium sulfate was used for drying, and vacuum drying was performed to obtain 774 mg of pure (R)-1-(naphthalen-1-yl)ethane-1-amine with 89% yield and 97% ee.

##STR00025##

[0069] In an argon atmosphere, 3-acetylphenylethyl(methyl)carbamate (1 mmol, 221 mg), Ru(OAc).sub.2L.sub.1 (0.2 mol %), NH.sub.4OAc (2 mmol, 154 mg) and trifluoroethanol (2 mL) were added into a 5 mL ampoule. A reaction flask was placed in an autoclave. Hydrogen was injected for replacement three times, wherein 10 atm of hydrogen was injected each time, and 50 atm of hydrogen was injected the last time. The autoclave was placed in an oil bath which was preheated in advance to a corresponding temperature, and heating stirring was performed for 20 hours. Cooling was performed to a room temperature. The hydrogen was slowly released, and the reaction flask was taken out. 3 mL of a 6 M hydrogen chloride solution was added, and heating was performed at 80° C. for 6 hours. Cooling was performed, and washing was performed with ethyl ether two times. A 4 M sodium hydroxide solution was used for neutralization till pH was 10. Extraction was performed with ethyl ether three times, and organic phases were combined. Anhydrous sodium sulfate was used for drying, and vacuum drying was performed to obtain 186 mg of pure (R)-3-(1-aminoethyl)phenylethyl(methyl)carbamate with 84% yield and 94% ee.

[0070] The above embodiments are preferred implementations of the present invention, but the implementations of the present invention are not limited by the above embodiments. Any other change, modification, substitution, combination and simplification without departing from the spiritual essence and principle of the present invention shall be equivalent replacement modes, which are contained in the protection scope of the present invention.