ASYMMETRIC HOMOGENEOUS HYDROGENATION OF IMINES USING RHODIUM PHOSPHINE SYSTEMS

被引:42
作者
CULLEN, WR
FRYZUK, MD
JAMES, BR
KUTNEY, JP
KANG, GJ
HERB, G
THORBURN, IS
SPOGLIARICH, R
机构
[1] Department of Chemistry, University of British Columbia, Vancouver, BC V6T 1Y6
来源
JOURNAL OF MOLECULAR CATALYSIS | 1990年 / 62卷 / 03期
基金
加拿大自然科学与工程研究理事会;
关键词
13;
D O I
10.1016/0304-5102(90)85220-C
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
An efficient, reproducible system for the asymmetric homogeneous catalytic hydrogenation of imines is presented. By optimization of a number of parameters, it has been found that the combination of a chiral bidentate phosphine having a two-carbon backbone such as cycphos (cycphos = 1,2-bis(diphenylphosphino)-1-cyclohexylethane) with a rhodium(I) precursor in methanol-benzene or methanol-toluene at pressures between 1000 and 1500 psi hydrogenates the imine ArNC(CH2OMe)CH3 (Ar = 2,6-dimethylphenyl or 2-methyl-6-ethylphenyl) in quantitative yield (reactions times range between 40 and 70 h) and with good enantioselectivity. The enantioselectivities range from 40 to 69% e.e. depending on the temperature, lower temperatures (-25°C) favouring the higher e.e. Some discussion of the mechanism is presented. © 1990.
引用
收藏
页码:243 / 253
页数:11
相关论文
共 23 条
  • [11] JAMES B, 1990, CATALYSIS ORGANIC RE, P11
  • [12] RHODIUM(I)-CATALYZED ASYMMETRIC HYDROGENATION OF IMINES
    KANG, GJ
    CULLEN, WR
    FRYZUK, MD
    JAMES, BR
    KUTNEY, JP
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1988, (22) : 1466 - 1467
  • [13] ASYMMETRIC REDUCTION OF CARBON-NITROGEN, CARBON-OXYGEN, AND CARBON-CARBON DOUBLE-BONDS BY HOMOGENEOUS CATALYTIC-HYDROGENATION
    LEVI, A
    MODENA, G
    SCORRANO, G
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1975, (01) : 6 - 7
  • [14] HYDROGENATION OF IMINES BY RHODIUM-PHOSPHINE COMPLEXES
    LONGLEY, CJ
    GOODWIN, TJ
    WILKINSON, G
    [J]. POLYHEDRON, 1986, 5 (10) : 1625 - 1628
  • [15] MARCH J, 1977, ADV ORG CHEM, P834
  • [16] MCCARTY CG, 1970, CHEM CARBON NITROGEN, P382
  • [17] THE INFLUENCE OF ATROPISOMERISM AND CHIRAL CENTER ON THE BIOLOGICAL-ACTIVITY OF METOLACHLOR
    MOSER, H
    RIHS, G
    SAUTER, H
    [J]. ZEITSCHRIFT FUR NATURFORSCHUNG SECTION B-A JOURNAL OF CHEMICAL SCIENCES, 1982, 37 (04): : 451 - 462
  • [18] MOSER H, 1977, Patent No. 4022611
  • [19] MOSER H, 1976, Patent No. 3937730
  • [20] RILEY DP, 1980, J ORG CHEM, V45, P5189