Enantiomerically pure rhodium complexes bearing 1,5-diphenyl-1,5-cyclooctadiene as a chiral diene ligand. Their use as catalysts for asymmetric 1,4-addition of phenylzinc chloride

Enantiomerically pure rhodium complexes bearing 1,5-diphenyl-1,5-cyclooctadiene as a chiral diene ligand. Their use as catalysts for asymmetric 1,4-addition of phenylzinc chloride
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DOI:
10.1021/ol0524914
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发表时间:
2005-12-22
期刊:
影响因子:
5.2
通讯作者:
Hayashi, T
Hayashi, T
中科院分区:
化学1区
文献类型:
--
作者:
Kina, A;Ueyama, K;Hayashi, T

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通过对非对映异构体[Rh(Ph-cod)((R)-1,1‘-binaphthyl-2,2’-diamine)]BF4.的光学拆分,得到了一种与1,5-二苯基-1,5-环辛二烯(Ph-Cod)配位的Rh配合物[RhCl((R)-Ph-Cod)](2)在氯三甲基硅烷存在下,苯基氯化锌与α,β-不饱和酮和酯的不对称1,4-加成反应中,具有高催化活性和对映体选择性(最高达98%ee)。
A rhodium complex coordinated with 1,5-diphenyl-1,5-cyclooctadiene (Ph-cod), [RhCl((R)-Ph-cod)](2), was obtained enantiomerically pure through optical resolution of diastereomeric isomers [Rh(Ph-cod)((R)-1,1'-binaphthyl-2,2'-diamine)]BF4. The enantiomerically pure rhodium complexes showed high catalytic activity and enantioselectivity (up to 98% ee) in the asymmetric 1,4-addition of phenylzinc chloride to alpha,beta-unsaturated ketones and esters in the presence of chlorotrimethylsilane.