CN108101740A - 一种芳香炔烃一锅法直接转化成手性醇的方法 - Google Patents
一种芳香炔烃一锅法直接转化成手性醇的方法 Download PDFInfo
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- 150000001345 alkine derivatives Chemical class 0.000 title claims abstract description 22
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- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims abstract description 17
- 235000019254 sodium formate Nutrition 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
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- 238000004128 high performance liquid chromatography Methods 0.000 description 22
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- ZYMCBJWUWHHVRX-UHFFFAOYSA-N (4-nitrophenyl)-phenylmethanone Chemical class C1=CC([N+](=O)[O-])=CC=C1C(=O)C1=CC=CC=C1 ZYMCBJWUWHHVRX-UHFFFAOYSA-N 0.000 description 2
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
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Abstract
本发明涉及一种芳香炔烃一锅法直接转化成手性醇的方法,该方法以廉价易得的炔烃I为原料,采用“两步一锅法”策略直接合成手性醇II,具体包括步骤1):以含氟的醇和水为溶剂,在三氟甲烷磺酸催化下发生水合反应生成中间体酮;步骤2):直接在反应体系中加入单磺酰手性二胺与金属钌或铑或铱的络合物为催化剂,以甲酸钠水溶液或者甲酸‑三乙胺的混合物为氢源,通过不对称转移氢化反应得到产物II。该方法操作简便,反应条件温和、底物适用范围广、对映选择性高。具体反应通式如下:
Description
技术领域
本发明属于不对称催化技术领域,具体涉及一种芳香炔烃一锅法直接转化成手性醇的方法。
背景技术
手性醇通常由酮的不对称还原或者酮与有机金属试剂不对称加成反应来制备,但是有些酮和有机金属试剂合成复杂,不易得到。炔烃是一类廉价易得的原料,从炔烃出发,采用“水合反应-不对称还原两步一锅法”策略直接合成手性醇的方法具有原子经济性和步骤经济性,符合绿色化学原则,具有重要应用前景。采用该策略实现炔烃直接转化成手性醇的方法已有报道,但是需要采用双金属催化体系,比如:(IPr)AuBF4]/Ru-TsDPEN(Chem.Commun.2017,53, 1638–1641),Co-Porphyrin/Rh-TsDPEN(J.Am.Chem.Soc.2015,137,12984–12989)。因此开发反应条件温和、操作简单、单金属催化体系具有更重要的应用价值。本发明报道一种以炔烃为原料,三氟乙醇为溶剂,20mol%三氟甲烷磺酸为催化剂,40℃反应4小时生成中间体酮,然后在反应体系中加入手性二胺金属络合物催化剂,不同比例的甲酸和三乙胺的混合物或甲酸钠水溶液为氢源,在40℃下发生不对称转移氢化合成手性醇。该方法具有反应条件简单、温和,底物适应范围广,对映选择性高等优点。
发明内容
本发明涉及一种芳香炔烃一锅法直接转化成手性醇的方法。该方法以炔烃为原料,采取“两步一锅法”策略,步骤1):以含氟的醇和水为溶剂,在布朗斯特酸催化下,多乙炔基取代的苯进行水合反应生成中间体酮;
步骤2):将中间体酮的反应体系中直接加入单磺酰手性二胺与金属钌或铑或铱的络合物为催化剂,以甲酸钠水溶液或者甲酸-三乙胺的混合物为氢源,通过不对称转移氢化反应得到产物 II;具体反应通式如下:
所述化合物I或II,Ar选自或
R是氢、C1-C3烷基、C1-C3烷基氧基、三氟甲基、氟、氯、溴、羟基、氨基、硝基、氰基中的任意一种;
上面给出的化合物I或II的定义中,所用术语不论单独使用还是用在复合词中,代表如下取代基:
卤素:指氟、氯、溴、碘;
烷基:指直链或支链烷基;
卤代烷基:指直链或支链烷基,在这些烷基上的氢原子部分或全部被卤原子取代。
所述步骤1):水合反应的溶剂为含氟醇和水的混合物,进一步优选为:1毫升三氟乙醇和2当量水或者1毫升六氟异丙醇和2当量水;
所述步骤1):水合反应的催化剂为布朗斯特酸,进一步优选为:20mol%三氟甲磺酸;
所述步骤1):水合反应的温度为25-70℃;反应时间为4-48小时;
所述步骤2):不对称转移氢化所用催化剂为(R,R)-或(S,S)-N-单磺酰-二芳基手性乙二胺与过渡金属钌或铑或者铱的配合物,其结构通式如式III、式IV所示,
所述结构通式III和IV中,M为Ru、Rh或Ir;
Ar为苯基或对甲氧基、甲基取代的苯基、萘基;
R为-CH3、-CF3、-C6H5、4-CH3C6H4、4-CF3C6H4、4-(t-Bu)-C6H4-、3,4-(CH3)2-C6H3-、 2,4,6-(CH3)3-C6H2-、2,6-Cl2-C6H3-、2,4,6-(i-Pr)3-C6H2-、C6F5、或萘基;
R’为H、CH3或i-Pr;
L为苯、1,4-二甲基苯、1-甲基-4-异丙基苯、1,3,5-三甲基苯、1,2,3,4,5-五甲基苯、1,2,3,4,5,6- 六甲基苯或五甲基环戊二烯;
X为Cl-、[OTf]-、[PF6]-、[BF4]-、[SbF6]-或手性磷酸阴离子;
Y为C或O。
所述步骤2):不对称转移氢化所用催化剂,进一步优选,代表性催化剂结构如下:
所述步骤2):不对称转移氢化,氢源为不同比例的甲酸和三乙胺的混合物或甲酸钠水溶液;进一步优选为:10当量的甲酸钠和1毫升水。
所述步骤2):不对称转移氢化,反应温度为25-80℃,进一步优选为:50℃。
所述步骤2):不对称转移氢化,反应时间为4-72小时。
本发明所涉及的一种芳香炔烃一锅法直接转化成手性醇的方法,该方法以廉价易得的炔烃I为原料,采用“两步一锅法”策略直接合成手性醇II。该方法操作简便,反应条件温和、底物适用范围广、对映选择性高。
具体实施方式
下面结合具体实施例,对本发明作进一步说明,但本发明并不限于以下实施例。
本发明中所用手性催化剂通用制备方法,以催化剂A合成为例:0.005mmol(S,S)-N-五氟苯磺酰二苯基手性乙二胺和0.0025mmol[Ru(cymene)]2Cl2溶解在0.5毫升二氯甲烷中,加入 0.005mmol三乙胺,室温下反应30分钟,水洗,水相用1毫升二氯甲烷萃取3次,合并后浓缩至干得到催化剂A,直接用于催化反应。
实施例1:(S)-1-苯乙醇的不对称合成
将0.5mmol的苯乙炔加入到试管中,依次加入CF3SO3H(20mol%,9uL),H2O(2equiv.,20 uL),CF3CH2OH(1mL),40℃反应4h后,加入0.005mmol催化剂A,HCOONa(0.5mmol,34mg, 2.5mmol,170mg),H2O(1mL),50℃反应5小时。反应结束后用乙酸乙酯萃取3次,合并有机相浓缩至干,分离产率:93%(石油醚:乙酸乙酯=5:1),HPLC测定产物(S)-1-苯乙醇的ee 值为97%的。HPLC分离条件:手性柱大赛璐OD-H-H柱,流动相:正己烷/异丙醇=97:3(体积比),流速:1.0毫升/分钟,波长:254纳米,柱温:30摄氏度,t1=11.58分钟,t2=13.82分钟;1H NMR(400MHz,CDCl3):δ=7.43-7.37(m,4H),7.34-7.30(m,1H),4.93(dd,J1=12.8Hz, J2=12.8Hz,1H),2.03(s,3H),1.54(d,J=6.4Hz,3H)ppm;13C NMR(100MHz,CDCl3):δ= 145.83,128.53,127.50,125.41,70.44,25.19ppm.
实施例2:(S)-1-苯乙醇的不对称合成
将0.5mmol的苯乙炔加入到试管中,依次加入CF3SO3H(20mol%,9uL),H2O(2equiv.,20 uL),CF3CH2OH(1mL),40℃反应4h后,加入0.005mmol催化剂B,HCOONa(0.5mmol,34 mg),H2O(1mL),50℃反应5小时。反应结束后用乙酸乙酯萃取3次,合并有机相浓缩至干,分离产率:41%(石油醚:乙酸乙酯=5:1),HPLC测定产物(S)-1-苯乙醇的ee值为93%的。
实施例3:(S)-1-苯乙醇的不对称合成
将0.5mmol的苯乙炔加入到试管中,依次加入CF3SO3H(20mol%,9uL),H2O(2equiv.,20 uL),CF3CH2OH(1mL),40℃反应4h后,加入0.005mmol催化剂D,HCOONa(0.5mmol,34 mg),H2O(1mL),50℃反应5小时。反应结束后用乙酸乙酯萃取3次,合并有机相浓缩至干,分离产率:68%(石油醚:乙酸乙酯=5:1),HPLC测定产物(S)-1-苯乙醇的ee值为95%的。
实施例4:(S)-1-苯乙醇的不对称合成
将0.5mmol的苯乙炔加入到试管中,依次加入CF3SO3H(20mol%,9uL),H2O(2equiv.,20 uL),CF3CH2OH(1mL),40℃反应4h后,加入0.005mmol催化剂E,HCOONa(0.5mmol,34 mg),H2O(1mL),50℃反应5小时。反应结束后用乙酸乙酯萃取3次,合并有机相浓缩至干,分离产率:48%(石油醚:乙酸乙酯=5:1),HPLC测定产物(S)-1-苯乙醇的ee值为79%的。
实施例5:(S)-1-苯乙醇的不对称合成
将0.5mmol的苯乙炔加入到试管中,依次加入CF3SO3H(20mol%,9uL),H2O(2equiv.,20 uL),CF3CH2OH(1mL),40℃反应4h后,加入0.005mmol催化剂A,HCOOH/TEA(摩尔比1.1:1, 1mL),50℃反应5小时。反应结束后用乙酸乙酯萃取3次,合并有机相浓缩至干,分离产率:69%(石油醚:乙酸乙酯=5:1),HPLC测定产物(S)-1-苯乙醇的ee值为95%的。
实施例6:(S)-1-(4-甲基苯基)乙醇的不对称合成
将0.5mmol的4-甲基苯乙炔加入到试管中,依次加入CF3SO3H(20mol%,9uL),H2O(2equiv.,20uL),CF3CH2OH(1mL),50℃反应6h后,加入0.005mmol催化剂A,HCOONa(0.5 mmol,34mg),H2O(1mL),50℃反应5小时。反应结束后用乙酸乙酯萃取3次,合并有机相浓缩至干,分离产率:83%(石油醚:乙酸乙酯=5:1),HPLC测定产物(S)-1-(4-甲基苯基)乙醇的ee值为98%的。HPLC分离条件:手性柱大赛璐OJ-H柱,流动相:正己烷/异丙醇=95:5(体积比),流速:1.0毫升/分钟,波长:220纳米,柱温:30摄氏度,t1=10.14分钟,t2=11.59分钟;1HNMR(400MHz,CDCl3):δ=7.31(dd,J1=6.0Hz,J2=6.0Hz,2H),7.21(t,J=8.0Hz, 2H),4.90(dd,J1=13.2Hz,J2=13.2Hz,1H),2.39(s,3H),1.97(s,1H),1.52(d,J=6.4Hz,3H) ppm;13C NMR(100MHz,CDCl3):δ=142.90,137.16,129.18,125.38,70.26,25.10,21.12ppm.
实施例7:(S)-1-苯己醇的不对称合成
将0.5mmol的1-苯己炔加入到试管中,依次加入CF3SO3H(20mol%,9uL),H2O(2equiv., 20uL),CF3CH2OH(1mL),50℃反应48h后,加入0.005mmol催化剂A,HCOONa(0.5mmol, 34mg),H2O(1mL),50℃反应5小时。反应结束后用乙酸乙酯萃取3次,合并有机相浓缩至干,分离产率:60%(石油醚:乙酸乙酯=5:1),HPLC测定产物(S)-1-苯己醇的ee值为81%的。HPLC分离条件:手性柱大赛璐OD-H柱,流动相:正己烷/异丙醇=99:1(体积比),流速: 1.0毫升/分钟,波长:220纳米,柱温:30摄氏度,t1=19.25分钟,t2=20.70分钟;1H NMR(400 MHz,CDCl3):δ=7.38(dd,J1=5.2Hz,J2=8.4Hz,2H),7.33-7.31(m,J=6.0Hz,2H),4.68(dd, J1=7.2Hz,J2=7.6Hz,1H),2.14(s,1H),1.77-1.73(m,1H),1.48-1.44(m,1H),1.37-1.31(m,5H), 0.92(dd,J1=6.4Hz,J2=6.4Hz,3H)ppm;13C NMR(100MHz,CDCl3):δ=145.00,128.42, 127.46,125.94,74.70,39.10,31.77,25.54,22.61,14.07ppm.
实施例8:(S)-1-(4-甲氧基苯基)乙醇的不对称合成
将0.5mmol的4-甲氧基苯乙炔加入到试管中,依次加入CF3SO3H(20mol%,9uL),H2O(2 equiv.,20uL),CF3CH2OH(1mL),40℃反应4h,加入0.005mmol催化剂A,HCOONa(0.5mmol,34mg),H2O(1mL),50℃反应5小时。反应结束后用乙酸乙酯萃取3次,合并有机相浓缩至干,分离产率:77%(石油醚:乙酸乙酯=5:1),HPLC测定产物(S)-1-(4-甲氧基苯基)乙醇的ee值为92%的。HPLC分离条件:手性柱大赛璐OD-H柱,流动相:正己烷/异丙醇=97:3(体积比),流速:1.0毫升/分钟,波长:254纳米,柱温:30摄氏度,t1=15.98分钟,t2=17.12分钟;1H NMR(400MHz,CDCl3):δ=7.32(dd,J1=6.4Hz,J2=6.4Hz,2H),6.91(dd,J1=6.8Hz, J2=6.4Hz,2H),4.86(dd,J1=12.8Hz,J2=12.8Hz,1H),3.83(s,3H),2.22(s,1H),1.50(d,J=6.4Hz,3H);13C NMR(100MHz,CDCl3):δ=158.92,138.07,126.70,113.83,69.93,55.31,25.05.
实施例9:(S)-1-(2-氯苯基)乙醇的不对称合成
将0.5mmol的2-氯苯乙炔加入到试管中,依次加入CF3SO3H(20mol%,9uL),H2O(2equiv.,20uL),CF3CH2OH(1mL),50℃反应12h后,加入0.005mmol催化剂A,HCOONa(0.5 mmol,34mg),H2O(1mL),50℃反应5小时。反应结束后用乙酸乙酯萃取3次,合并有机相浓缩至干,分离产率:88%(石油醚:乙酸乙酯=5:1),HPLC测定产物(S)-1-(2-氯苯基)乙醇的ee值为87%的。HPLC分离条件:手性柱大赛璐OD-H柱,流动相:正己烷/异丙醇=99:1(体积比),流速:1.0毫升/分钟,波长:220纳米,柱温:30摄氏度,t1=20.65分钟,t2=22.23分钟;1H NMR(400MHz,CDCl3):δ=7.38-7.32(m,2H),7.26-7.22(m,1H),5.33(dd,J1=6.8Hz,J2=6.8Hz,1H),2.04(s,1H),1.53(d,J=6.4Hz,3H)ppm;13C NMR(100MHz,CDCl3):δ=143.05,131.665,129.43,128.44127.24,126.42,67.01,23.54.
实施例10:(S)-1-(4-氯苯基)乙醇的不对称合成
将0.5mmol的4-氯苯乙炔加入到试管中,依次加入CF3SO3H(20mol%,9uL),H2O(2equiv.,20uL),CF3CH2OH(1mL),40℃反应24h,加入0.005mmol催化剂A,HCOONa(0.5 mmol,34mg),H2O(1mL),50℃反应5小时。反应结束后用乙酸乙酯萃取3次,合并有机相浓缩至干,分离产率:75%(石油醚:乙酸乙酯=5:1),HPLC测定产物(S)-1-(4-氯苯基)乙醇的ee值为92%的。HPLC分离条件:手性柱大赛璐OD-H柱,流动相:正己烷/异丙醇=97:3(体积比),流速:1.0毫升/分钟,波长:220纳米,柱温:30摄氏度,t1=10.73分钟,t2=11.91分钟;1H NMR(400MHz,CDCl3):δ=7.37-7.32(m,4H),4.90(dd,J1=12.8Hz,J2=12.8Hz,1H), 2.05(s,1H),1.50(d,J=6.4Hz,3H)ppm;13C NMR(100MHz,CDCl3):δ=144.25,133.07, 128.61,126.81,69.75,25.29ppm.
实施例11:(S)-1-(4-硝基苯基)乙醇的不对称合成
将0.5mmol的4-硝基苯乙炔加入到试管中,依次加入CF3SO3H(20mol%,9uL),H2O(2equiv.,20uL),(CF3)2CHOH(1mL),50℃反应24h后,加入0.005mmol催化剂A,HCOONa(0.5mmol,34mg),H2O(1mL),50℃反应5小时。反应结束后用乙酸乙酯萃取3次,合并有机相浓缩至干,分离产率:66%(石油醚:乙酸乙酯=5:1),HPLC测定产物(S)-1-(4-硝基苯基)乙醇的ee值为86%的。HPLC分离条件:手性柱大赛璐OJ-H柱,流动相:正己烷/异丙醇=95:5(体积比),流速:1.0毫升/分钟,波长:254纳米,柱温:30摄氏度,t1=30.88分钟,t2=34.17分钟;1H NMR(400MHz,CDCl3):δ=8.21(dd,J1=6.8Hz,J2=6.8Hz,2H),7.57-7.55(m,2H), 5.03(dd,J1=14.2Hz,J2=14.2Hz,1H),2.37(s,1H),1.54(d,J=6.4Hz,3H)ppm;13C NMR(100MHz,CDCl3):δ=153.17,147.13,126.15,123.76,69.50,25.51ppm.
实施例12:(S)-1-(2,5-二氯苯基)乙醇的不对称合成
将0.5mmol的2,5-二氯苯乙炔加入到试管中,依次加入CF3SO3H(20mol%,9uL),H2O(2 equiv.,20uL),CF3CH2OH(1mL),50℃反应24h后,加入0.005mmol催化剂A,HCOONa(0.5mmol,34mg),H2O(1mL),50℃反应5小时。反应结束后用乙酸乙酯萃取3次,合并有机相浓缩至干,分离产率:79%(石油醚:乙酸乙酯=5:1),HPLC测定产物(S)-1-(2,5-二氯苯基) 乙醇的ee值为86%,HPLC分离条件:手性柱大赛璐OD-H柱,流动相:正己烷/异丙醇=99:1(体积比),流速:1.0毫升/分钟,波长:220纳米,柱温:30摄氏度,t1=19.90分钟,t2=21.43 分钟;1H NMR(400MHz,CDCl3):δ=7.51(d,J=8.4Hz,1H),7.34(d,J=6.0Hz,1H),7.27(dd, J1=8.4Hz,J2=8.4Hz,1H),5.22(dd,J1=12.8Hz,J2=12.8Hz,1H),2.78(s,1H),1.45(d,J=6.4Hz,3H)ppm;13C NMR(100MHz,CDCl3):δ=141.72,133.34,132.09,129.06,127.48,127.41,66.50,23.58ppm.
实施例13:(S)-1-萘乙醇的不对称合成
将0.5mmol的2-萘乙炔加入到试管中,依次加入CF3SO3H(20mol%,9uL),H2O(2equiv., 20uL),CF3CH2OH(1mL),50℃反应24h后,加入0.005mmol催化剂A,HCOONa(0.5mmol, 34mg),H2O(1mL),50℃反应5小时,反应结束后用乙酸乙酯萃取3次,合并有机相浓缩至干,分离产率:89%(石油醚:乙酸乙酯=5:1),HPLC测定产物(S)-1-萘乙醇的ee值为88%, HPLC分离条件:手性柱大赛璐OJ-H柱,流动相:正己烷/异丙醇=95:5(体积比),流速:1.0 毫升/分钟,波长:230纳米,柱温:30摄氏度,t1=23.63分钟,t2=31.74分钟;1H NMR(400 MHz,CDCl3):δ=7.89-7.85(m,4H),7.56-7.49(m,3H),5.13-5.08(m,1H),2.08(d,J=3.2Hz, 1H),1.62(d,J=6.4Hz,3H)ppm;13C NMR(100MHz,CDCl3):δ=143.21,133.39,132.94, 128.34,127.96,127.70,126.18,125.83,123.85,123.83,70.56,25.17ppm。
Claims (9)
1.一种芳香炔烃一锅法直接转化成手性醇的方法,其特征在于,包括如下步骤:
步骤1):以含氟的醇和水为溶剂,在布朗斯特酸催化下,多乙炔基取代的苯进行水合反应生成中间体酮;
步骤2):将中间体酮的反应体系中直接加入单磺酰手性二胺与金属钌或铑或铱的络合物为催化剂,以甲酸钠水溶液或者甲酸-三乙胺的混合物为氢源,通过不对称转移氢化反应得到产物II;具体反应通式如下:
2.权利要求1所述的芳香炔烃一锅法直接转化成手性醇的方法,其特征在于,
所述的Ar选自
R是氢、C1-C10烷基、C1-C10烷基氧基、卤代烷基、卤素、羟基、氨基、硝基、氰基、芳基中的任意一种;
上面给出的化合物I或II的定义中,所用术语不论单独使用还是用在复合词中,代表如下取代基:
卤素:指氟、氯、溴、碘;
烷基:指直链或支链烷基;
卤代烷基:指直链或支链烷基,在这些烷基上的氢原子部分或全部被卤原子取代。
3.权利要求1所述的芳香炔烃一锅法直接转化成手性醇的方法,其特征在于,所述的含氟醇和水的混合物溶剂包括三氟乙醇、六氟异丙醇。
4.权利要求1所述的芳香炔烃一锅法直接转化成手性醇的方法,其特征在于,所述的布朗斯特酸博客三氟乙酸、三氟甲磺酸。
5.权利要求1所述的芳香炔烃一锅法直接转化成手性醇的方法,其特征在于,所述的水合反应温度为25-70℃。
6.权利要求1所述的芳香炔烃一锅法直接转化成手性醇的方法,其特征在于,
(R,R)-或(S,S)-N-单磺酰-二芳基手性乙二胺与过渡金属钌或铑或者铱的络合物,其结构通式如式III、式IV所示,
所述结构通式III和IV中,M为Ru、Rh或Ir;
Ar为苯基或对甲氧基、甲基取代的苯基、萘基;
R为-CH3、-CF3、-C6H5、4-CH3C6H4、4-CF3C6H4、4-(t-Bu)-C6H4-、3,4-(CH3)2-C6H3-、2,4,6-(CH3)3-C6H2-、2,6-Cl2-C6H3-、2,4,6-(i-Pr)3-C6H2-、C6F5、或萘基;
R’为H、CH3或i-Pr;
L为苯、1,4-二甲基苯、1-甲基-4-异丙基苯、1,3,5-三甲基苯、1,2,3,4,5-五甲基苯、1,2,3,4,5,6-六甲基苯或五甲基环戊二烯;
X为Cl-、[OTf]-、[PF6]-、[BF4]-、[SbF6]-或手性磷酸阴离子;
Y为C或O。
7.权利要求1所述的芳香炔烃一锅法直接转化成手性醇的方法,其特征在于,单磺酰手性二胺与金属钌或铑或铱的配合物的具体结构如下:
中的任意一种。
8.权利要求1所述的芳香炔烃一锅法直接转化成手性醇的方法,其特征在于,甲酸与三乙胺的质量比为任意比。
9.权利要求1所述的芳香炔烃一锅法直接转化成手性醇的方法,其特征在于,所述的不对称转移氢化反应温度为25-80℃。
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