Direct and enantioselective α-allylation of ketones via singly occupied molecular orbital (SOMO) catalysis

被引：90

作者：

Mastracchio, Anthony ^{[1
]}

Warkentin, Alexander A. ^{[1
]}

Walji, Abbas M. ^{[1
]}

MacMillan, David W. C. ^{[1
]}

机构：

[1] Princeton Univ, Merck Ctr Catalysis, Princeton, NJ 08544 USA

来源：

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA | 2010年 / 107卷 / 48期

关键词：

asymmetric synthesis; organocatalysis; ALLYLIC ALKYLATION; ALDEHYDES;

D O I：

10.1073/pnas.1002845107

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

The first enantioselective organocatalytic alpha-allylation of cyclic ketones has been accomplished via singly occupied molecular orbital catalysis. Geometrically constrained radical cations, forged from the one-electron oxidation of transiently generated enamines, readily undergo allylic alkylation with a variety of commercially available allyl silanes. A reasonable latitude in both the ketone and allyl silane components is readily accommodated in this new transformation. Moreover, three new oxidatively stable imidazolidinone catalysts have been developed that allow cyclic ketones to successfully participate in this transformation. The new catalyst platform has also been exploited in the first catalytic enantioselective alpha-enolation and alpha-carbooxidation of ketones.

引用

页码：20648 / 20651

页数：4

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