Stereloselective Ring Expansion of Vinyl Oxiranes: Mechanistic Insights and Natural Product Total Synthesis

被引：35

作者：

Brichacek, Matthew ^{[1
]}

Batory, Lindsay A. ^{[1
]}

Njardarson, Jon T. ^{[1
]}

机构：

[1] Cornell Univ, Dept Chem & Chem Biol, Baker Lab, Ithaca, NY 14853 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2010年 / 49卷 / 09期

基金：

美国国家科学基金会;

关键词：

copper; natural products; oxiranes; stereoselectivity; total synthesis; BIS(OXAZOLINYL)PYRIDINE-SCANDIUM(III) TRIFLATE COMPLEXES; FRIEDEL-CRAFTS ALKYLATIONS; STEREOSELECTIVE-SYNTHESIS; STYRYL-LACTONE; (+)-GONIOTHALESDIOL; REARRANGEMENT; COPPER; DERIVATIVES; CORE; DIOL;

D O I：

10.1002/anie.200906830

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

"Chemical Equation Presented" What a (strain) relief! The first broadly applicable, catalytic, and stereoselective vinyl oxirane ring expansion is described (see scheme; hfacac = hexafluoroacetylacetonate). The stereoselectivity was influenced by several reaction parameters, and kinetic studies support a mechanistic proposal involving the in situ formation of a more reactive catalytic species. This ring-expansion reaction has been employed in the asymmetric total synthesis of (+)-goniothalesdiol. © 2010 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

页码：1648 / 1651

页数：4

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