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手性钌双环配合物:酮的快速、对映选择性和广泛范围氢化的前催化剂。

Chiral ruthenabicyclic complexes: precatalysts for rapid, enantioselective, and wide-scope hydrogenation of ketones.

机构信息

Division of Chemical Process Engineering, Faculty of Engineering, Hokkaido University, Sapporo, Hokkaido 060-8628, Japan.

出版信息

J Am Chem Soc. 2011 Jul 20;133(28):10696-9. doi: 10.1021/ja202296w. Epub 2011 Jun 23.

DOI:10.1021/ja202296w
PMID:21675799
Abstract

A novel ruthenabicyclic complex with base shows excellent catalytic activity in the asymmetric hydrogenation of ketones. The turnover frequency of the hydrogenation of acetophenone reaches about 35,000 min(-1) in the best case, affording 1-phenylethanol in >99% ee. Several aliphatic and base-labile ketones are smoothly converted to the corresponding alcohols in high enantioselectivity. The catalytic cycle for this hydrogenation, in which the ruthenabicyclic structure of the catalyst is maintained, is proposed on the basis of the deuteration experiment and spectroscopic analysis data.

摘要

一种新型的钌双环配合物与碱表现出在酮的不对称氢化中优异的催化活性。在最佳情况下,苯乙酮的氢化的周转频率达到约 35000 min(-1),提供了>99%ee 的 1-苯乙醇。几种脂肪族和碱性不稳定的酮在高对映选择性下顺利转化为相应的醇。基于氘代实验和光谱分析数据,提出了该氢化反应的催化循环,其中催化剂的钌双环结构得以保持。

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