Asymmetric synthesis of cyclic α-amino acid derivatives by the intramolecular reaction of magnesium carbenoid with an N-magnesio arylamine

被引：28

作者：

Mitsunaga, Shintaro ^{[1
]}

Ohbayashi, Tohru ^{[1
]}

Sugiyama, Shimpei ^{[1
]}

Saitou, Takahito ^{[1
]}

Tadokoro, Makoto ^{[1
]}

Satoh, Tsuyoshi ^{[1
]}

机构：

[1] Tokyo Univ Sci, Fac Sci, Dept Chem, Shinjuku Ku, Tokyo 1620826, Japan

来源：

TETRAHEDRON-ASYMMETRY | 2009年 / 20卷 / 14期

关键词：

LITHIO ARYLAMINES; DIASTEREOSELECTIVE SYNTHESIS; SUBSTITUTED CARBANIONS; TERT-BUTYLLITHIUM; METHYL-ESTERS; GENERATION; SULFOXIDES; KETONES; ALDEHYDES; AZIRIDINYLLITHIUMS;

D O I：

10.1016/j.tetasy.2009.06.024

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The synthesis of pipecolic acid and homopipecolic acid derivatives was developed from omega-(2-aminophenyl)-1-chloroalkyl p-tolyl sulfoxides by treatment with i-PrMgCl. An intramolecular nucleophilic substitution reaction of a magnesium carbenoid with an N-magnesio arylamine is the key step of this reaction. Proline and pipecolic acid derivatives were also synthesized from omega-(arylamino)-1-chloroalkyl p-tolyl sulfoxides by the same chemistry. Starting from enantiomerically pure (1S,R-s)-1-chloro-3-[2-(N-methylamino)phenyl]propyl p-tolyl sulfoxide, enantiomerically pure (R)-pipecolic acid derivative was obtained. The intramolecular nucleophilic substitution reaction of the magnesium carbenoid with N-magnesio arylamine was proven to take place with inversion of the carbenoid carbon. The stereochemistry of these reactions is also discussed. (C) 2009 Elsevier Ltd. All rights reserved.

引用

页码：1697 / 1708

页数：12

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