区域选择性铑催化 1,3-二烯的氢甲酰化反应，得到具有二氮杂磷杂环戊烷配体的高对映选择性的β,γ-不饱和醛。

Regioselective rhodium-catalyzed hydroformylation of 1,3-dienes to highly enantioenriched β,γ-unsaturated aldehyes with diazaphospholane ligands.

机构信息

Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, United States.

出版信息

Org Lett. 2011 Jan 7;13(1):164-7. doi: 10.1021/ol102797t. Epub 2010 Dec 6.

DOI:10.1021/ol102797t

PMID:21133397

Abstract

Regioselective and enantioselective rhodium-catalyzed hydroformylation of 1,3-dienes with chiral bisdiazaphospholane ligands yields β,γ-unsaturated aldehydes that retain a C═C functionality for further conversion. The reaction conditions are mild, featuring low catalyst loadings (0.5 mol %), pressures readily obtained in glass bottles, and convenient reaction times (1.5-12 h). Optimized reaction conditions produce high enantioselectivity (>90% ee), regioselectivity (88-99%), and conversion to β,γ-unsaturated aldehydes (99%) for ten 1,3-dienes encompassing a variety of substitution patterns.

摘要

手性双二氮杂膦烷配体的铑催化 1,3-二烯的区域和对映选择性氢甲酰化反应生成保留 C═C 官能团以进一步转化的 β,γ-不饱和醛。反应条件温和，催化剂负载量低（0.5 mol%），在玻璃瓶中很容易获得压力，反应时间方便（1.5-12 h）。优化的反应条件为十种 1,3-二烯提供了高对映选择性（>90%ee）、区域选择性（88-99%）和 β,γ-不饱和醛的转化率（99%），这些二烯具有各种取代模式。