SUCCESSFUL APPLICATION OF A FORGOTTEN PHOSPHINE IN ASYMMETRIC CATALYSIS - A 9-PHOSPHABICYCLO[3.3.1]NON-9-YL FERROCENE DERIVATIVE AS CHIRAL LIGAND

被引:74
作者
ABBENHUIS, HCL
BURCKHARDT, U
GRAMLICH, V
KOLLNER, C
PREGOSIN, PS
SALZMANN, R
TOGNI, A
机构
[1] ETH ZURICH,INORGAN CHEM LAB,CH-8092 ZURICH,SWITZERLAND
[2] ETH ZURICH,INST CRYSTALLOG & PETROG,CH-8092 ZURICH,SWITZERLAND
关键词
D O I
10.1021/om00002a025
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The technical mixture ''phobane'', containing the two isomers 9-phospha-9H-bicyclo[3.3.1]-nonane (3a) and 9-phospha-9H-bicyclo[4.2.1]nonane (3b) in a similar to 2:1 ratio was reacted with N,N-dimethyl-(S)-1-[(R)-2-(diphenylphosphino)ferrocenyl]ethylamine (4) in acetic acid. The clean amine substitution product is the new chiral biphosphine 5. When only 2 equiv of 3 were reacted with 4, a 4:1 mixture of the two isomeric products 5a and 5b were obtained. However, the use of a 10-fold excess of 3 afforded the pure [3,3,1]-isomer 5a, 9-phospha-9-[(S)-1-{(R)-2-(diphenylphosphino)ferrocenyl}ethyl][3.3.1]bicyclononane, in 68% isolated yield. (S)-(R)-5a crystallizes in the orthorhombic space group P2(1)2(1)2(1), Z = 4, a = 7.393(3) Angstrom, b = 19.261(5) Angstrom, and c = 19.546(8) Angstrom. 5a was used in the asymmetric Pd-catalyzed alkylation of 1,3-diphenyl-3-acetoxypropene with dimethyl malonate. Enantioselectivities up to 85% ee were obtained. The cationic Pd-allyl complexes [Pd(eta(3)-C3H5)(5a)]O3SCF3 (6) and [Pd(eta(3)-PhCHCHCHPh)(5a)]O3SCF3 (7) were prepared and characterized by X-ray diffraction, Complex 6 crystallizes in the monoclinic space group P2(1), Z = 2, a = 9.162(4) Angstrom, b = 16.069(5) Angstrom, c = 11.816(5) Angstrom, and beta = 96.86(3)degrees. Crystalline 7 was obtained as a CH2Cl2 monosolvate and belongs to the triclinic system: space group P1, Z = 1, a = 11.07(2) Angstrom, b = 11.216(14) Angstrom, c = 11.888(16) Angstrom, alpha = 62.37(9)degrees, beta = 65.96(11)degrees, and gamma = 70.29(11)degrees. The ligand assumes very different conformations in its complexes, as compared to the free state. Multidimensional (31)p, C-13, and H-1 NMR studies reveal that 7 exists in solution as a mixture of four isomers. Aspects of the selective equilibria were elucidated using P-31- and H-1-exchange spectroscopy.
引用
收藏
页码:759 / 766
页数:8
相关论文
共 20 条
  • [1] A NEW STEROSELECTIVE APPROACH TO CHIRAL FERROCENYL LIGANDS FOR ASYMMETRIC CATALYSIS
    ABBENHUIS, HCL
    BURCKHARDT, U
    GRAMLICH, V
    TOGNI, A
    ALBINATI, A
    MULLER, B
    [J]. ORGANOMETALLICS, 1994, 13 (11) : 4481 - 4493
  • [2] TABLES OF BOND LENGTHS DETERMINED BY X-RAY AND NEUTRON-DIFFRACTION .1. BOND LENGTHS IN ORGANIC-COMPOUNDS
    ALLEN, FH
    KENNARD, O
    WATSON, DG
    BRAMMER, L
    ORPEN, AG
    TAYLOR, R
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1987, (12): : S1 - S19
  • [3] TRANS-INFLUENCE - ITS MEASUREMENT AND SIGNIFICANCE
    APPLETON, TG
    CLARK, HC
    MANZER, LE
    [J]. COORDINATION CHEMISTRY REVIEWS, 1973, 10 (3-4) : 335 - 422
  • [4] 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
  • [5] PREPARATION OF A NOVEL P-P-BONDED DIPHOSPHINE
    HARRIS, TV
    PRETZER, WR
    [J]. INORGANIC CHEMISTRY, 1985, 24 (25) : 4437 - 4439
  • [6] KLAUI W, 1989, INORG CHEM, V28, P3845
  • [7] Mason RF, 1968, Patent No. 3400163
  • [8] TABLES OF BOND LENGTHS DETERMINED BY X-RAY AND NEUTRON-DIFFRACTION .2. ORGANOMETALLIC COMPOUNDS AND CO-ORDINATION COMPLEXES OF THE D-BLOCK AND F-BLOCK METALS
    ORPEN, AG
    BRAMMER, L
    ALLEN, FH
    KENNARD, O
    WATSON, DG
    TAYLOR, R
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1989, (12): : S1 - S83
  • [9] SCHNYDER A, IN PRESS ANGEW CHEM
  • [10] ASSIGNMENT OF THE P-31 AND H-1 RESONANCES IN OLIGONUCLEOTIDES BY TWO-DIMENSIONAL NMR-SPECTROSCOPY
    SKLENAR, V
    MIYASHIRO, H
    ZON, G
    MILES, HT
    BAX, A
    [J]. FEBS LETTERS, 1986, 208 (01) : 94 - 98