Theoretical evidence for oxygenated intermediates in the reductive cyclization of nitrobenzenes

被引：76

作者：

Davies, IW ^{[1
]}

Guner, VA

Houk, KN

机构：

[1] Merck & Co Inc, Dept Proc Res, Rahway, NJ 07065 USA

[2] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA

来源：

ORGANIC LETTERS | 2004年 / 6卷 / 05期

关键词：

D O I：

10.1021/ol0364273

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Deoxygenation of nitroaromatics is a classic synthetic method for the construction of nitrogen heterocycles. The generally accepted mechanism involves exhaustive deoxygenation to a singlet nitrene. We present theoretical evidence for an alternative, 6pi-electron 5-atom electrocyclization of nitroso-styrenes, -stilbenes, and -biphenyls to nitronates. A downstream 1,5-H shift and tautomerization leads to N-hydroxy heterocycles.

引用

页码：743 / 746

页数：4

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