Part III. COD versus NBD precatalysts. Dramatic difference in the asymmetric hydrogenation of prochiral olefins with five-membered diphosphine Rh-hydrogenation catalysts

被引:67
作者
Drexler, HJ [1 ]
Baumann, W [1 ]
Spannenberg, A [1 ]
Fischer, C [1 ]
Heller, D [1 ]
机构
[1] Univ Rostock, Inst Organ Katalyseforsch, D-18055 Rostock, Germany
关键词
D O I
10.1016/S0022-328X(00)00756-7
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Induction periods in the asymmetric hydrogenation of prochiral olefins with five-membered chelates of the type [Rh(PP)(diolefin)]BF4 originate from the parallel-running hydrogenation of the prochiral substrate and the diolefin that enters the system as a constituent of the precatalyst. Reactivities towards the most commonly used diolefins COD or NBD can differ by three powers of ten. X-ray crystal structure analyses of [Rh((S,S)-Et-DuPHOS)(NBD)]BF4 and of [Rh((R,R)-Et-DuPHOS)(COD)]BF4 imply that a recently discussed relation between the sense of rotation of the diolefin in the precatalyst (clockwise or anticlockwise twist) is not very likely. (C) 2001 Elsevier Science B.V. All rights reserved.
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页码:89 / 102
页数:14
相关论文
共 97 条
[51]  
HELLER D, 1995, LIEBIGS ANN, P575
[52]   Influence of a remote hydroxy group in the ligand on the reactivity of a chiral hydrogenation catalyst [J].
Heller, D ;
Holz, J ;
Borns, S ;
Spannenberg, A ;
Kempe, R ;
Schmidt, U ;
Borner, A .
TETRAHEDRON-ASYMMETRY, 1997, 8 (02) :213-222
[53]   Kinetic models for catalytic selection processes as applied to asymmetric hydrogenation [J].
Heller, D ;
Thede, R ;
Haberland, D .
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 1997, 115 (02) :273-281
[54]  
HELLER D, 1998, THESIS EMST MORITZ A
[55]   Synthesis of a new class of functionalized chiral bisphospholane ligands and the application in enantioselective hydrogenations [J].
Holz, J ;
Quirmbach, M ;
Schmidt, U ;
Heller, D ;
Stürmer, R ;
Börner, A .
JOURNAL OF ORGANIC CHEMISTRY, 1998, 63 (22) :8031-8034
[56]   Synthesis of the first water-soluble chiral tetrahydroxy diphosphine Rh(I) catalyst for enantioselective hydrogenation [J].
Holz, J ;
Heller, D ;
Stürmer, R ;
Börner, A .
TETRAHEDRON LETTERS, 1999, 40 (39) :7059-7062
[57]   P-chiral bis(trialkylphosphine) ligands and their use in highly enantioselective hydrogenation reactions [J].
Imamoto, T ;
Watanabe, J ;
Wada, Y ;
Masuda, H ;
Yamada, H ;
Tsuruta, H ;
Matsukawa, S ;
Yamaguchi, K .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (07) :1635-1636
[58]  
JIANG Q, 1998, ANGEW CHEM, V110, P1203
[59]  
Jiang QZ, 1998, ANGEW CHEM INT EDIT, V37, P1100, DOI 10.1002/(SICI)1521-3773(19980504)37:8<1100::AID-ANIE1100>3.0.CO
[60]  
2-3