Novel chiral ligands, diferrocenyl dichalcogenides and their derivatives, for rhodium- and iridium-catalyzed asymmetric hydrosilylation

被引:120
作者
Nishibayashi, Y
Segawa, K
Singh, JD
Fukuzawa, S
Ohe, K
Uemura, S
机构
[1] KYOTO UNIV,GRAD SCH ENGN,DIV ENERGY & HYDROCARBON CHEM,SAKYO KU,KYOTO 60601,JAPAN
[2] CHUO UNIV,FAC SCI & ENGN,BUNKYO KU,TOKYO 112,JAPAN
关键词
D O I
10.1021/om950533u
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
As chiral ligands for transition metal complex-catalyzed asymmetric reactions, a variety of novel chiral ferrocenyl chalcogen compounds, which possess planar chirality due to the 1,2-unsymmetrically disubstituted ferrocene structure, have been prepared from chiral ferrocenes. There are seven diferrocenyl dichalcogenides (4-10), nine alkyl or aryl ferrocenyl chalcogenides (11-19), two bis(ferrocenylseleno)alkanes (20 and 21), two 1-(phenylchalcogeno)-1-[2-(diphenylphosphino)ferrocenyl]ethanes (22 and 24), and two 1-(phenylchalcogeno)-1-[1',2-bis(diphenylphosphino)ferrocenyl]ethanes (23 and 25). 2,3-O,O'-Isopropylidene-2,3-dihydroxy-1,4-bis(phenylchalcogeno)butanes (26-28) are also synthesized. The Rh(I) complex-catalyzed hydrosilylation of ketones with diphenylsilane in the presence of these chiral ligands including the reported [R,S;R,S]-bis[2-[1-(dimethylamino)ethyl]ferrocenyl]dichalcogenides (1-3), followed by hydrolysis with dilute HCl, affords the corresponding chiral alcohols (R-configuration) in moderate to quantitative yield with up to 88% enantiomeric excess (ee), Similar treatment of acetophenone in the presence of diferrocenyl dichalcogenides (1, 2, 3, and 10) and a catalytic amount of Ir(I) complex gives chiral 1-phenylethanol of the opposite configuration (S) compared with the Rh case in high yield with up to 23% ee. The new complex prepared from a cationic rhodium compound and the diferrocenyl diselenide (2) shows an activity for asymmetric hydrosilylation of acetophenone to afford 1-phenylethanol in 60% chemical yield with 60% ee. Asymmetric hydrosilylation of imines and asymmetric hydrogenation of an enamide also proceed smoothly using the Rh(I)-diselenide (2) catalytic system to give the corresponding sec-amines and amide with up to 53% and 69% ee, respectively. A catalytic cycle involving the formation of tetracoordinated rhodium(I)-dichalcogenide complex (two Se and two N atoms to one Rh) followed by oxidative addition of the Si-H bond to Rh(I) and carbonyl addition to the produced rhodium(III) hydride complex is proposed for hydrosilylation of ketones.
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页码:370 / 379
页数:10
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  • [1] ASYMMETRIC CATALYZES .28. ENANTIOSELECTIVE HYDROSILYLATION OF PROCHIRAL 3,4-DIHYDRO-2H-PYRROLE DERIVATIVES
    BECKER, R
    BRUNNER, H
    MAHBOOBI, S
    WIEGREBE, W
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1985, 24 (11): : 995 - 996
  • [2] STERICALLY HINDERED CHALCOGENOLATO COMPLEXES - MONO-MERIC AND DI-MERIC THIOLATES AND SELENOLATES OF ZINC AND CADMIUM - STRUCTURE OF ((CD(SEC6H2BUT3-2,4,6)2)2), THE 1ST 3-CO-ORDINATE CADMIUM SELENIUM COMPLEX
    BOCHMANN, M
    WEBB, KJ
    HURSTHOUSE, MB
    MAZID, M
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1991, (09): : 2317 - 2323
  • [3] AN UNUSUAL, SELECTIVE ETA(3)-ETA(1) ALLYL ISOMERIZATION IN A CHIRAL ALLYLIC ALKYLATION CATALYST
    BREUTEL, C
    PREGOSIN, PS
    SALZMANN, R
    TOGNI, A
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (09) : 4067 - 4068
  • [4] ASYMMETRIC CATALYSIS .45. ENANTIOSELECTIVE HYDROSILYLATION OF KETONES WITH [RH(COD)CL]2/PYRIDINYLOXAZOLINE CATALYSTS
    BRUNNER, H
    OBERMANN, U
    [J]. CHEMISCHE BERICHTE-RECUEIL, 1989, 122 (03): : 499 - 507
  • [5] ASYMMETRIC SYNTHESES .20. ENANTIOSELECTIVE HYDROSILYLATION OF KETONES WITH [RH(COD)CL]2 THIAZOLIDINE CATALYSTS
    BRUNNER, H
    BECKER, R
    RIEPL, G
    [J]. ORGANOMETALLICS, 1984, 3 (09) : 1354 - 1359
  • [6] Brunner H., 1991, TETRAHEDRON-ASYMMETR, P931
  • [7] BRUNNER H, 1993, CATALYTIC ASYMMETRIC, pCH6
  • [8] Brunner H., 1993, HDB ENANTIOSELECTIVE
  • [9] THIOLATO AND SELENIDO COMPLEXES OF RHODIUM(III)
    COLLMAN, JP
    ROTHROCK, RK
    STARK, RA
    [J]. INORGANIC CHEMISTRY, 1977, 16 (02) : 437 - 440
  • [10] ASYMMETRIC CATALYTIC REDUCTION WITH TRANSITION-METAL COMPLEXES .2. ASYMMETRIC CATALYSIS BY A SUPPORTED CHIRAL RHODIUM COMPLEX
    DUMONT, W
    POULIN, J
    DANG, T
    KAGAN, HB
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1973, 95 (25) : 8295 - 8299