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接力铁/手性 Brønsted 酸催化:苯并恶嗪酮的对映选择性氢化。

Relay iron/chiral Brønsted acid catalysis: enantioselective hydrogenation of benzoxazinones.

机构信息

CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University , 152 Luoyu Road, Wuhan 430079, P. R. China.

出版信息

J Am Chem Soc. 2015 Feb 25;137(7):2763-8. doi: 10.1021/jacs.5b00085. Epub 2015 Feb 13.

DOI:10.1021/jacs.5b00085
PMID:25587941
Abstract

An asymmetric hydrogenation reaction of benzoxazinones has been accomplished via a relay iron/chiral Brønsted acid catalysis. This approach provides a variety of chiral dihydrobenzoxazinones in good to high yields (75-96%) and enantioselectivities (up to 98:2 er). It is noteworthy that challenging 3-alkyl-substituted substrates underwent highly enantioselective reduction. A key to success is the utilization of a nonchiral phosphine ligand to reduce disadvantageous background reactions through tuning the catalytic activity of Fe3(CO)12.

摘要

通过接力铁/手性 Brønsted 酸催化,实现了苯并恶嗪酮的不对称氢化反应。该方法以良好到优秀的收率(75-96%)和对映选择性(高达 98:2 er)提供了各种手性二氢苯并恶嗪酮。值得注意的是,具有挑战性的 3-烷基取代底物经历了高度对映选择性还原。成功的关键是利用非手性膦配体通过调节 Fe3(CO)12 的催化活性来减少不利的背景反应。

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