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用于酮的高效催化不对称转移氢化的铁(II)配合物。

Iron(II) complexes for the efficient catalytic asymmetric transfer hydrogenation of ketones.

作者信息

Meyer Nils, Lough Alan J, Morris Robert H

机构信息

Department of Chemistry, University of Toronto, 80 St. George St., Toronto, ON, M5S 3H6, Canada.

出版信息

Chemistry. 2009;15(22):5605-10. doi: 10.1002/chem.200802458.

DOI:10.1002/chem.200802458
PMID:19360823
Abstract

Iron(II) carbonyl compounds of the type trans-[Fe(NCMe)(CO)(P-N-N-P)]BF(4) bearing the ethylenediamine-derived diiminodiphosphine ligands (R,R)- or (S,S)-1,2-diphenyl-1,2-diaminoethane were synthesized and characterized, including by their crystal structures. The new complexes are suitable precatalysts for the transfer hydrogenation of ketones at room temperature, giving turnover frequencies of up to 2600 h(-1) with low catalyst loadings (0.025-0.17%). Screening experiments showed that the precatalysts are able to produce alcohols from a wide range of simple ketones. For sterically demanding prochiral ketones, excellent enantioselectivities were obtained (up to 96% ee).

摘要

合成并表征了带有乙二胺衍生的二亚氨基二膦配体(R,R)-或(S,S)-1,2-二苯基-1,2-二氨基乙烷的反式-[Fe(NCMe)(CO)(P-N-N-P)]BF(4) 型羰基铁(II)化合物,包括通过其晶体结构进行表征。这些新配合物是室温下酮转移氢化反应的合适预催化剂,在低催化剂负载量(0.025 - 0.17%)下,周转频率高达2600 h(-1)。筛选实验表明,这些预催化剂能够从多种简单酮制备醇。对于空间位阻较大的前手性酮,获得了优异的对映选择性(高达96% ee)。

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