阅读说明：本技术 一种合成仲醇的方法 (Method for synthesizing secondary alcohol ) 是由 李峰 胥婧 王荣周 于 2019-08-20 设计创作，主要内容包括：本发明公开了一种合成仲醇的方法,其步骤为：在反应容器中,加入酮,过渡金属催化剂,甲醇；反应混合物在水浴中加热,反应数小时后,冷却到室温,旋转蒸发除去溶剂,然后通过柱分离,得到目标化合物。本发明用酮做原料,使用甲醇作氢源和溶剂,在过渡金属催化剂的参与下,通过氢转移,生成伯醇,反应展现出三个显著的优点：1)不加碱；2)反应温度低；3)反应原子经济。(The invention discloses a method for synthesizing secondary alcohol, which comprises the following steps: adding ketone, transition metal catalyst and methanol into a reaction container; the reaction mixture was heated in a water bath, after several hours of reaction, cooled to room temperature, the solvent was removed by rotary evaporation, and then separated by column to give the target compound. The method takes ketone as a raw material, takes methanol as a hydrogen source and a solvent, generates primary alcohol through hydrogen transfer in the presence of a transition metal catalyst, and has three remarkable advantages: 1) no alkali is added; 2) the reaction temperature is low; 3) the reaction atoms are economical.)

1. A process for the synthesis of secondary alcohols comprising

From ketones II

A step of generating a target product I through hydrogenation reaction in the presence of a transition metal catalyst,

wherein R is¹Selected from alkyl, aryl, mono-or polysubstituted aryl；

R²Selected from methyl, ethyl or C₉Alkyl, phenyl, benzyl.

2. The method of claim 1, wherein the mono-or poly-substituted aryl group comprises any one of methylphenyl, methoxyphenyl, trifluoromethylphenyl, and halophenyl groups.

3. The process of claim 1 wherein the catalyst is an iridium complex having the structure:

。

4. the process according to claim 1, wherein the amount of catalyst used is 1 mol% relative to the ketone.

5. The process of claim 1, wherein the hydrogenation reaction uses methanol as a hydrogen source.

6. The method of claim 5, wherein the ratio of ketone to methanol is 1:2 mmol/mL.

7. The method of claim 1, wherein the reaction is carried out at 66 ± 2 ℃.

8. The method of claim 1, wherein the reaction time is not less than 12 hours.

Technical Field

The invention belongs to the technical field of organic synthetic chemistry, and particularly relates to a method for synthesizing secondary alcohol.

Background

Secondary alcohols are important compounds, not only are important organic intermediates, but also are widely applied to fine chemical engineering aspects such as medicines, pesticides, spices and the like. In the traditional methods, high-temperature and high-pressure hydrogenation can be used, and the methods have potential safety hazards in the reaction process.

In recent years, methanol, a cheap, safe and non-toxic hydrogen donor, has received much attention as a hydrogen source for preparation. However, a strong or weak base needs to be added during the reaction. (a) Yu, z.; zeng, f.; sun, x.; deng, h.; dong, j.; chen, j.; wang, h.; pei, c.j.organometallic.chem.2007,692,2306-2313 (b) Bigler, r.; huber, r.; mezzetti, a.angelw.chem.int.ed.2015, 54,1-5 Moore, c.m.; (c) szymczak, n.k.chem.commu., 2013,49, 400-; yamaga, T.Ishii Y.J.org.chem.2001,66, 4710-; puerta, m.c.; valerga, p. organometallics 2012,31, 6868-; niu, j.; yang, m.; li, Z.; wu, l.; hao, x.; song, M.organometallics 2015,34,1170-1176.

Therefore, from the perspective of organic synthesis, a new class of organometallic catalysts is developed, which can catalyze such reactions in an environmentally friendly and mild state by using inexpensive, safe and nontoxic methanol as a hydrogen source and a solvent without adding an alkali to the reaction.

Disclosure of Invention

The invention aims to provide a method for synthesizing secondary alcohol.

The invention is realized by the following technical scheme: a process for the synthesis of secondary alcohols of formula I comprising

From ketones (formula II)

And (4) obtaining a target product through hydrogenation reaction.

The reaction takes place in the presence of a transition metal catalyst and has the general formula

Wherein R is¹Is selected from alkyl, aryl, and mono-or poly-substituted aryl, wherein the mono-or poly-substituted aryl is preferably methylphenyl, methoxyphenyl, trifluoromethylphenyl, and halophenyl;

R²represents a substituent selected from methyl, ethyl or C₉Alkyl, phenyl, benzyl.

The novel method for synthesizing the secondary alcohol is realized by the following specific steps:

adding ketone, transition metal catalyst and methanol into a reaction container; the reaction mixture was heated in a water bath, after several hours of reaction, cooled to room temperature, the solvent was removed by rotary evaporation, and then separated by column to give the target compound.

Further, the transition metal catalyst is a metal-organic bifunctional anionic iridium complex containing a bipyridyl ligand, and the structure of the metal-organic bifunctional anionic iridium complex is as follows:

further, the transition metal catalyst is used in an amount of 1 mol% based on the ketone.

Further, the ratio of ketone to methanol was 1:2 mmol/mL.

Further, the reaction time is not less than 12 hours.

Further, the reaction temperature was 66 ℃.

Compared with the prior art, the method takes ketone as a raw material, takes methanol as a hydrogen source and a solvent, and generates the primary alcohol through hydrogen transfer in the presence of a transition metal catalyst. The reaction exhibits three significant advantages: 1) no alkali is added; 2) the reaction temperature is low; 3) the reaction atoms are economical.

Detailed Description

The following examples are shown to illustrate certain embodiments of the present invention and should not be construed as limiting the scope of the invention. Many modifications, variations and changes in materials, methods and reaction conditions may be made simultaneously with respect to the disclosure herein. All such modifications, variations and changes are intended to fall within the spirit and scope of the present invention.

Example 1-Phenylethanol

1-phenylethanol

Mixing acetophenone (120mg,1.0mmol) and cat [ Ir ]](5.7mg,0.01mmol,1 mol%) and methanol (2mL) were added sequentially to a 25mL Kjeldahl tube, N₂Protecting, and reacting at 66 ℃ for 12 h. Cooling to room temperature, rotary evaporation to remove the solvent, and then column chromatography (developing solvent: petroleum ether/ethyl acetate) gives the pure title compound in the following yields: 87 percent of

¹H NMR(500MHz,CDCl₃)δ7.37-7.33(m,4H),7.28-7.25(m,1H),4.89(q,J＝6.3Hz,1H),1.96(br s,1H),1.49(d,J＝6.5Hz,3H)；¹³C NMR(125MHz,CDCl₃)δ145.8,128.5,127.4,125.3,70.4,25.1.

Example 2 3-Methylphenylethanol

1-m-tolylethanol

Mixing 3-methylacetophenone (134mg,1.0mmol) with cat [ Ir ]](5.7mg,0.01mmol,1 mol%) and methanol (2mL) were added sequentially to a 25mL Kjeldahl tube, N₂Protecting, and reacting at 66 ℃ for 12 h. Cooling to room temperature, rotary evaporation to remove the solvent, and then column chromatography (developing solvent: petroleum ether/ethyl acetate) gives the pure title compound in the following yields: 78 percent of

¹H NMR(500MHz,CDCl₃)δ7.24-7.22(m,1H),7.17(s,1H),7.15(d,J＝7.7Hz,1H),7.08(d,J＝7.5Hz,1H),4.84-4.81(m,1H),2.35(s,3H),2.03(br s,1H),1.47(d,J＝6.5Hz,3H)；¹³C NMR(125MHz,CDCl₃)δ145.8,138.1,128.4,128.1,126.1,122.4,70.3,25.0,21.4.

Example 3 4-Methylphenylethanol

1-p-tolylethanol

Mixing 4-methylacetophenone (134mg,1.0mmol) with cat [ Ir ]](5.7mg,0.01mmol,1 mol%) and methanol (2mL) were added sequentially to a 25mL Kjeldahl tube, N₂Protecting, and reacting at 66 ℃ for 12 h. Cooling to room temperature, rotary evaporation to remove the solvent, and then column chromatography (developing solvent: petroleum ether/ethyl acetate) gives the pure title compound in the following yields: 84 percent

¹H NMR(500MHz,CDCl₃)δ7.25(d,J＝8.0Hz,2H),7.15(d,J＝7.8Hz,2H),4.95-4.83(m,1H),2.33(s,3H),1.95(br s,1H),1.47(d,J＝6.5Hz,3H)；¹³C NMR(125MHz,CDCl₃)δ142.8,137.1,129.1,125.3,70.2,25.0,21.0.

Example 4 Ethylphenethyl alcohol

1-(4-ethylphenyl)ethanol

4-ethyl acetophenone (148mg,1.0mmol) and cat [ Ir ]](5.7mg,0.01mmol,1 mol%) and methanol (2mL) were added sequentially to a 25mL Kjeldahl tube, N₂Protecting, and reacting at 66 ℃ for 12 h. Cooling to room temperature, rotary evaporation to remove the solvent, and then column chromatography (developing solvent: petroleum ether/ethyl acetate) gives the pure title compound in the following yields: 81 percent of

¹H NMR(500MHz,CDCl₃)δ7.30(d,J＝8.0Hz,2H),7.19(d,J＝8.0Hz,2H),4.88-4.86(m,1H),2.65(q,J＝7.6Hz,2H),1.79(br s,1H),1.49(d,J＝6.5Hz,3H),1.23(t,J＝7.6Hz,3H)；¹³C NMR(125MHz,CDCl₃)δ143.6,143.1,128.0,125.4,70.3,28.5,25.0,15.6.

Example 5 3-Methoxyphenylethanol

1-(3-Methoxyphenyl)ethanol

Mixing 3-methoxyacetophenone (150mg,1.0mmol) and cat [ Ir ]](5.7mg,0.01mmol,1 mol%) and methanol (2mL) were added sequentially to a 25mL Kjeldahl tube, N₂Protecting, and reacting at 66 ℃ for 12 h. Cooling to room temperature, rotary evaporation to remove the solvent, and then column chromatography (developing solvent: petroleum ether/ethyl acetate) gives the pure title compound in the following yields: 82 percent of

¹H NMR(500MHz,CDCl₃)δ7.26(t,J＝5.7Hz,1H),6.95-6.93(m,1H),6.82(dd,J＝8.3Hz and 2.5Hz,1H),4.89-4.87(m,1H),3.82(s,3H),1.86(br s,1H),1.50(d,J＝6.5Hz,3H)；¹³C NMR(125MHz,CDCl₃)δ159.7,147.6,129.4,117.6,112.8,110.9,70.2,55.1,25.1.

Example 6 3-Fluorophenylethanol

1-(3-Fluorophenyl)ethanol

Mixing 3-fluoro acetophenone (138mg,1.0mmol) and cat [ Ir ]](5.7mg,0.01mmol,1 mol%) and methanol (2mL) were added sequentially to a 25mL Kjeldahl tube, N₂Protecting, and reacting at 66 ℃ for 12 h. Cooling to room temperature, rotary evaporation to remove the solvent, and then column chromatography (developing solvent: petroleum ether/ethyl acetate) gives the pure title compound in the following yields: 94 percent of

¹H NMR(500MHz,CDCl₃)δ7.29(q,J＝7.9Hz,1H),7.13-7.08(m,2H),6.95(td,J＝8.4and 2.3Hz,1H),4.91-4.86(m,1H),2.02(br s,1H),1.48(d,J＝6.5Hz,3H)；¹³C NMR(125MHz,CDCl₃)δ164.0(d,J_C-F＝244.5Hz),148.5(d,J＝6.4Hz),130.0(d,J＝8.1Hz),120.9,114.3(d,J＝21.1Hz),112.4(d,J＝21.7Hz).

Example 7 4-Fluorophenylethanol

1-(4-fluorophenyl)ethanol

Mixing 4-fluoro acetophenone (138mg,1.0mmol) and cat [ Ir ]](5.7mg,0.01mmol,1 mol%) and methanol (2mL) were added sequentially to a 25mL Kjeldahl tube, N₂Protecting, and reacting at 66 ℃ for 12 h. Cooling to room temperature, rotary evaporation to remove the solvent, and then column chromatography (developing solvent: petroleum ether/ethyl acetate) gives the pure title compound in the following yields: 90 percent of

¹H NMR(500MHz,CDCl₃)δ7.33-7.31(m,2H),7.03-7.00(m,2H),4.87-4.86(m,1H),2.09(br s,1H),1.47(d,J＝6.5Hz,3H)；¹³C NMR(125MHz,CDCl₃)δ163.0(d,J_C-F＝243.8Hz),141.5,127.0(d,J＝8.0Hz),115.3(d,J_C-F＝21.1Hz),69.7,25.2.

Example 8 4-Chlorobenzeneethanol

1-(4-chlorophenyl)ethanol

Mixing 4-chloroacetophenone (155mg,1.0mmol) and cat [ Ir ]](5.7mg,0.01mmol,1 mol%) and methanol (2mL) were added sequentially to a 25mL Kjeldahl tube, N₂Protecting, and reacting at 66 ℃ for 12 h. Cooling to room temperature, rotary evaporation to remove the solvent, and then column chromatography (developing solvent: petroleum ether/ethyl acetate) gives the pure title compound in the following yields: 92 percent of

¹H NMR(500MHz,CDCl₃)δ7.32-7.29(m,4H),4.90-4.85(m,1H),1.93(br s,1H),1.47(d,J＝6.4Hz,3H)；¹³C NMR(125MHz,CDCl₃)δ144.2,133.1,128.6,126.8,68.7,25.2.

Example 92, 4-Dichlorophenethyl alcohol

1-(2,4-Dichlorophenyl)ethanol

Mixing 2, 4-dichloroacetophenone (189mg,1.0mmol) and cat [ Ir ]](5.7mg,0.01mmol,1 mol%) and methanol (2mL) were added sequentially to a 25mL Kjeldahl tube, N₂Protecting, and reacting at 66 ℃ for 12 h. Cooling to room temperature, rotary evaporation to remove the solvent, and then column chromatography (developing solvent: petroleum ether/ethyl acetate) gives the pure title compound in the following yields: 94 percent of

¹H NMR(500MHz,CDCl₃)δ7.54(d,J＝8.4Hz,1H),7.34(d,J＝2.0Hz,1H),7.28-7.26(m,1H),5.24-5.22(m,1H),2.10(br s,1H),1.46(d,J＝6.4Hz,3H)；¹³C NMR(125MHz,CDCl₃)δ141.7,133.4,132.1,129.1,127.5,127.4,66.6,23.6.

Example 10 3-Bromobenzene ethanol

1-(3-bromophenyl)ethanol

Mixing 3-bromoacetophenone (199mg,1.0mmol) and cat [ Ir ]](5.7mg,0.01mmol,1 mol%) and methanol (2mL) were added sequentially to a 25mL Kjeldahl tube,N₂protecting, and reacting at 66 ℃ for 12 h. Cooling to room temperature, rotary evaporation to remove the solvent, and then column chromatography (developing solvent: petroleum ether/ethyl acetate) gives the pure title compound in the following yields: 88 percent

¹H NMR(500MHz,CDCl₃)δ7.53(s,1H),7.40(d,J＝7.9Hz,1H),7.29(d,J＝7.7Hz,1H),7.21(t,J＝7.8Hz,1H),4.87-4.85(m,1H),1.95(br s,1H),1.48(dd,J＝6.5and 1.5Hz,3H)；¹³C NMR(125MHz,CDCl₃)δ148.1,130.5,130.1,128.6,124.0,122.6,69.7,25.2.

Example 11 4-Bromobenzene ethanol

1-(4-bromophenyl)ethanol

4-bromoacetophenone (199mg,1.0mmol) and cat [ Ir](5.7mg,0.01mmol,1 mol%) and methanol (2mL) were added sequentially to a 25mL Kjeldahl tube, N₂Protecting, and reacting at 66 ℃ for 12 h. Cooling to room temperature, rotary evaporation to remove the solvent, and then column chromatography (developing solvent: petroleum ether/ethyl acetate) gives the pure title compound in the following yields: 92 percent of

¹H NMR(500MHz,CDCl₃)δ7.47(d,J＝8.4Hz,2H),7.24(d,J＝8.3Hz,2H),4.86-4.84(m,1H),2.0(br s,1H),1.46(d,J＝6.5Hz,3H)；¹³C NMR(125MHz,CDCl₃)δ144.7,131.5,1127.1,121.1,69.7,25.2.

Example 12 4-Trifluoromethylphenylethanol

4-trifluoromethylacetophenone (188mg,1.0mmol) and cat [ Ir ]](5.7mg,0.01mmol,1 mol%) and methanol (2mL) were added sequentially to a 25mL Kjeldahl tube, N₂Protecting, and reacting at 66 ℃ for 12 h. Cooling to room temperature, rotary evaporation to remove the solvent, and then column chromatography (developing solvent: petroleum ether/ethyl acetate) gives the pure title compound in the following yields: 90 percent of

¹H NMR(500MHz,CDCl₃)δ7.59(d,J＝6.7Hz,2H),7.45(d,J＝8.2Hz,2H),4.92(q,J＝6.5Hz,1H),2.51(br s,1H),1.47(d,J＝6.5Hz,3H)；¹³C NMR(125MHz,CDCl₃)δ149.7,129.7(q,J_C-F＝32.2Hz),125.6,125.4,123.1(q,J_C-F＝270.3Hz),69.7,25.2.

Example 13 4-Nitrophenylethanol

1-(4-nitrophenyl)ethanol

Mixing 4-nitroacetophenone (165mg,1.0mmol) and cat [ Ir ]](5.7mg,0.01mmol,1 mol%) and methanol (2mL) were added sequentially to a 25mL Kjeldahl tube, N₂Protecting, and reacting at 66 ℃ for 12 h. Cooling to room temperature, rotary evaporation to remove the solvent, and then column chromatography (developing solvent: petroleum ether/ethyl acetate) gives the pure title compound in the following yields: 92 percent of

¹H NMR(500MHz,CDCl₃)δ8.21(d,J＝8.6Hz,2H),7.56(d,J＝8.6Hz,2H),5.04-5.02(m.1H),2.08(br s,1H),1.53(d,J＝6.6Hz,3H)；¹³C NMR(125MHz,CDCl₃)δ153.0,147.2,126.1,123.7,69.5,25.5.

Example 14 4-cyanophenylethanol

4-(1-hydroxyethyl)benzonitrile

Mixing 4-cyanoacetophenone (145mg,1.0mmol) and cat [ Ir ]](5.7mg,0.01mmol,1 mol%) and methanol (2mL) were added sequentially to a 25mL Kjeldahl tube, N₂Protecting, and reacting at 66 ℃ for 12 h. Cooling to room temperature, rotary evaporation to remove the solvent, and then column chromatography (developing solvent: petroleum ether/ethyl acetate) gives the pure title compound in the following yields: 93 percent

¹H NMR(500MHz,CDCl₃)δ7.64(d,J＝8.2Hz,2H),7.50(d,J＝8.2Hz,2H),4.97-4.95(m,1H),2.17(br s,1H),1.50(d,J＝6.6Hz,3H)；¹³C NMR(125MHz,CDCl₃)δ151.1,132.3,126.0,118.8,111.0,69.6,25.4.

Example 15 methyl 4- (1-hydroxyethyl) benzoic acid

Methyl 4-(1-hydroxyethyl)benzoate

Methyl 4-acetylbenzoate (178mg,1.0mmol) and cat [ Ir](5.7mg,0.01mmol,1 mol%) and methanol (2mL) were added sequentially to a 25mL Kjeldahl tube, N₂Protecting, and reacting at 66 ℃ for 12 h. Cooling to room temperature, rotary evaporation to remove the solvent, and then column chromatography (developing solvent: petroleum ether/ethyl acetate) gives the pure title compound in the following yields: 86 percent of the total weight

¹H NMR(500MHz,CDCl₃)δ7.95(d,J＝8.3Hz,2H),7.39(d,J＝8.2Hz,2H),4.90(q,J＝5.9Hz,1H),3.88(s,3H),2.91(brs,1H),1.46(d,J＝6.5Hz,3H)；¹³C NMR(125MHz,CDCl₃)δ167.0,151.0,129.7,128.8,125.2,69.7,52.0,25.1.

Example 16 2- (1-hydroxyethyl) pyridine

1-(pyridin-2-yl)ethanol

2-acetylpyridine (121mg,1.0mmol), cat [ Ir](5.7mg,0.01mmol,1 mol%) and methanol (2mL) were added sequentially to a 25mL Kjeldahl tube, N₂Protecting, and reacting at 66 ℃ for 12 h. Cooling to room temperature, rotary evaporation to remove the solvent, and then column chromatography (developing solvent: petroleum ether/ethyl acetate) gives the pure title compound in the following yields: 96 percent

¹H NMR(500MHz,CDCl₃)δ8.51(d,J＝4.1Hz,1H),7.68(td,J＝7.6and 1.5Hz,1H),7.32(d,J＝8.1Hz,1H),7.19-7.16(m,1H),4.92-4.87(m,1H),4.63(br s,1H),1.51(d,J＝6.9Hz,3H)；¹³C NMR(125MHz,CDCl₃)δ163.3,148.0,136.7,122.1,119.7,68.9,24.1.

Example 17 Naphthaleneethanol

1-(naphthalen-2-yl)ethanol

Mixing 2-acetonaphthone (170mg,1.0mmol) and cat [ Ir ]](5.7mg,0.01mmol,1 mol%) and methanol (2mL) were added sequentially to a 25mL Kjeldahl tube, N₂Protecting, and reacting at 66 ℃ for 12 h. Cooling to room temperature, rotary evaporation to remove the solvent, and then column chromatography (developing solvent: petroleum ether/ethyl acetate) gives the pure title compound in the following yields: 90 percent of

¹H NMR(500MHz,CDCl₃)δ7.85-7.81(m,4H),7.51-7.46(m,3H),5.10-5.06(m,1H),1.91(br s,1H),1.59(d,J＝6.5Hz,3H)；¹³C NMR(125MHz,CDCl₃)δ143.2,13.3,132.9,128.3,127.9,127.6,126.1,125.8,123.8,70.5,25.1.

Example 18 1-Phenylpropanols

1-phenylpropan-1-ol

Mixing 1-propiophenone (134mg,1.0mmol) and cat [ Ir ]](5.7mg,0.01mmol,1 mol%) and methanol (2mL) were added sequentially to a 25mL Kjeldahl tube, N₂Protecting, and reacting at 66 ℃ for 12 h. Cooling to room temperature, rotary evaporation to remove the solvent, and then column chromatography (developing solvent: petroleum ether/ethyl acetate) gives the pure title compound in the following yields: 88 percent

¹H NMR(500MHz,CDCl₃)δ7.35-7.34(m,4H),7.29-7.26(m,1H),4.61-4.68(m,1H),1.90(br s,1H),1.85-1.72(m,2H),0.91(t,J＝7.4Hz,3H)；¹³C NMR(125MHz,CDCl₃)δ144.6,128.4,127.5,125.9,76.0,31.9,10.1.

Example 19 1-Phenylbutanol

1-phenylbutan-1-ol

1-phenylbutanone (148mg,1.0mmol) and cat [ Ir](5.7mg,0.01mmol,1 mol%) and methanol (2mL) were added sequentially to a 25mL Kjeldahl tube, N₂Protecting, and reacting at 66 ℃ for 12 h. Cooling to room temperature, rotary evaporation to remove the solvent, and then column chromatography (developing solvent: petroleum ether/ethyl acetate) gives the pure title compound in the following yields: 87 percent of

¹H NMR(500MHz,CDCl₃)δ7.34-7.33(m,4H),7.28-7.25(m,1H),4.67(t,J＝6.7Hz,1H),1.91(br s,1H),1.82-1.75(m,1H),1.71-1.64(m,1H),1.47-1.39(m,1H),1.35-1.25(m,1H),0.93(t,J＝7.4Hz,3H)；¹³C NMR(125MHz,CDCl₃)δ144.9,128.4,127.4,125.9,74.4,41.2,19.0,13.9.

Example 20 Diphenylcarbinol

Diphenylmethanol

Benzophenone (182mg,1.0mmol), cat [ Ir](5.7mg,0.01mmol,1 mol%) and methanol (2mL) were added sequentially to a 25mL Kjeldahl tube, N₂Protecting, and reacting at 66 ℃ for 12 h. Cooling to room temperature, rotary evaporation to remove the solvent, and then column chromatography (developing solvent: petroleum ether/ethyl acetate) gives the pure title compound in the following yields: 93 percent

¹H NMR(500MHz,CDCl₃)δ7.38-7.31(m,8H),7.27-7.24(m,2H),5.83(s,1H),2.24(br s,1H)；¹³C NMR(125MHz,CDCl₃)δ143.8,128.5,127.6,126.5,76.3.

Example 21 2-dodecanol

dodecan-2-ol

Mixing 2-dodecanone (184mg,1.0mmol) and cat [ Ir ]](5.7mg,0.01mmol,1 mol%) and methanol (2)mL) were added sequentially to 25mL Kelvin, N₂Protecting, and reacting at 66 ℃ for 12 h. Cooling to room temperature, rotary evaporation to remove the solvent, and then column chromatography (developing solvent: petroleum ether/ethyl acetate) gives the pure title compound in the following yields: 78 percent of

¹H NMR(500MHz,CDCl₃)δ3.82-3.76(m,1H),1.46-1.40(m,4H),1.31-1.26(m,15H),1.19(d,J＝6.2Hz,3H),0.88(t,J＝6.9Hz,3H)；¹³C NMR(125MHz,CDCl₃)δ68.2,39.4,31.9,29.6,29.6,29.3,25.8,23.5,22.7,14.1.

Example 22 cyclohexanol

Cyclohexanol

Cyclohexanone (98mg,1.0mmol), cat [ Ir ]](5.7mg,0.01mmol,1 mol%) and methanol (2mL) were added sequentially to a 25mL Kjeldahl tube, N₂Protecting, and reacting at 66 ℃ for 12 h. Cooling to room temperature, rotary evaporation to remove the solvent, and then column chromatography (developing solvent: petroleum ether/ethyl acetate) gives the pure title compound in the following yields: 80 percent of

¹H NMR(500MHz,CDCl₃)δ3.57(m,1H),3.20(br s,1H),1.89(s,2H),1.72(s,2H),1.54(m,1H),1.24(m,4H),1.16(m,1H)；¹³C NMR(125MHz,CDCl₃)δ69.9,35.2,25.3,24.0.

Example 231, 3-Diphenylpropan-1-ol

1,3-Diphenylpropan-1-ol

Mixing 3-phenylbenzylketone (210mg,1.0mmol) and cat [ Ir ]](5.7mg,0.01mmol,1 mol%) and methanol (2mL) were added sequentially to a 25mL Kjeldahl tube, N₂Protecting, and reacting at 66 ℃ for 12 h. Cooling to room temperature, rotary evaporation to remove the solvent, and then column chromatography (developing solvent: petroleum ether/ethyl acetate) gives the pure title compound in the following yields: 83 percent

¹H NMR(500MHz,CDCl₃)δ7.35-7.34(m,4H),7.28-7.24(m,3H),7.19-7.16(m,3H),4.69-4.66(m,1H),2.77-2.63(m,2H),2.16-2.00(m,2H),1.92(br s,1H)；¹³C NMR(125MHz,CDCl₃)δ144.6,141.8,128.5,128.4,128.4,127.6,125.9,125.8,73.9,40.5,32.0.

Example 24 4-phenyl-2-butanol

4-phenylbutan-2-ol

4-phenyl-2-butanone (148mg,1.0mmol) and cat [ Ir](5.7mg,0.01mmol,1 mol%) and methanol (2mL) were added sequentially to a 25mL Kjeldahl tube, N₂Protecting, and reacting at 66 ℃ for 12 h. Cooling to room temperature, rotary evaporation to remove the solvent, and then column chromatography (developing solvent: petroleum ether/ethyl acetate) gives the pure title compound in the following yields: 80 percent of

¹H NMR(500MHz,CDCl₃)δ7.29-7.26(m,2H),7.20-7.16(m,3H),3.85-3.79(m,1H),2.78-2.63(m,2H),1.81-1.71(m,2H),1.57(br s,1H),1.23(d,J＝6.2Hz,3H)；¹³C NMR(125MHz,CDCl₃)δ142.0,128.3,125.8,67.4,40.8,32.1,23.5.。