A method for the synthesis of cyclopropanes by regiospecific and regioselective magnesium carbenoid 1,3-CH insertion as the key reactions

被引：14

作者：

Watanabe, Hiroyuki ^{[1
]}

Ogata, Shingo ^{[1
]}

Satoh, Tsuyoshi ^{[1
]}

机构：

[1] Tokyo Univ Sci, Grad Sch Chem Sci & Technol, Shinjuku Ku, Tokyo 1620826, Japan

来源：

TETRAHEDRON | 2010年 / 66卷 / 30期

关键词：

Cyclopropane; 1,3-CH insertion reaction; Magnesium carbenoid; Regiospecific reaction; Regioselective reaction; INCLUDING ASYMMETRIC-SYNTHESIS; P-TOLYL SULFOXIDE; 1ST EXAMPLE; CYCLIC-KETONES; COMPONENTS; GENERATION; CHEMISTRY; REARRANGEMENT; ENANTIOMERS; ARYLAMINES;

D O I：

10.1016/j.tet.2010.05.061

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Addition reaction of two geometrical isomers of 1-chlorovinyl p-tolyl sulfoxides, derived from unsymmetrical ketones and chloromethyl p-tolyl sulfoxide, with lithium enolate of tert-butyl acetate gave single diastereomers of the adduct, respectively. Treatment of each diastereomer with i-PrMgCl resulted in the formation of magnesium carbenoid. Highly regiospecific 1,3-CH insertion reaction was found to take place from each magnesium carbenoid to afford cyclopropanes. On the other hand, when the unsymmetrical ketones bearing an oxygen- or a nitrogen-functional group on the alpha-carbon were used in this procedure, the regioselective 1,3-CH insertion reaction proceeded mainly. Stereochemistry of the adducts, reaction mechanism, and essence of the specificity and the selectivity are discussed. (C) 2010 Elsevier Ltd. All rights reserved.

引用

页码：5675 / 5686

页数：12

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