Understanding the Reactivity of Acyl Anion Equivalents: The Epoxide Ring Opening Case

被引：11

作者：

Eger, Wilhelm A. ^{[1
]}

Grange, Rebecca L. ^{[1
]}

Schill, Heiko ^{[1
]}

Goumont, Regis ^{[2
]}

Clark, Timothy ^{[3
,4
]}

Williams, Craig M. ^{[1
]}

机构：

[1] Univ Queensland, Sch Chem & Mol Biosci, Brisbane, Qld 4072, Australia

[2] Univ Versailles, Inst Lavoisier Franklin, F-78035 Versailles, France

[3] Univ Erlangen Nurnberg, Comp Chem Ctr, D-91052 Erlangen, Germany

[4] Univ Erlangen Nurnberg, Interdisciplinary Ctr Mol Mat, D-91052 Erlangen, Germany

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2011年 / 2011卷 / 13期

关键词：

Umpolung; Epoxides; Acyl anion equivalent; Carbonyl equivalent; ALPHA-METALATED ISOCYANIDES; ION-PAIR ACIDITIES; SULFONYLMETHYL ISOCYANIDES; OXIDATIVE DECARBOXYLATION; NEGATIVE HYPERCONJUGATION; 1,3-DITHIANE DERIVATIVES; BROAD APPLICABILITY; DENSITY FUNCTIONALS; SYNTHETIC REACTIONS; EFFICIENT SYNTHESIS;

D O I：

10.1002/ejoc.201001680

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Acyl anion equivalents (umpolung) are the practitioner's first choice en route to 1,3-hydroxy keto compounds from epoxides. Why? This investigation evaluates computationally and experimentally the reactivity of a near comprehensive range of acyl anion equivalents using epoxide ring opening as a test vehicle. Reactivity understanding, reactivity order, surprise failures in performance, along with unprecedented, but far from superior, reactivity of TosMIC is presented for the first time.

引用

页码：2548 / 2553

页数：6

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