不对称串联 Wittig 重排/Mannich 反应。

Asymmetric tandem Wittig rearrangement/Mannich reactions.

机构信息

Department of Chemistry, University of Michigan, Ann Arbor, 48109-1055, USA.

出版信息

Angew Chem Int Ed Engl. 2010 Apr 6;49(16):2922-4. doi: 10.1002/anie.201000609. Epub 2010 Mar 15.

DOI:10.1002/anie.201000609

PMID:20232436

Abstract

The choice is yours: a highly stereoselective synthesis of α-alkyl-α-hydroxy-β-amino esters is accomplished through a tandem Wittig-rearrangement/Mannich reaction sequence. Transformations of N-benzyl or N-Boc imines proceed with high selectivity for formation of syn-amino alcohol derivatives, whereas N-Boc-2-(phenylsulfonyl)amines generate anti-amino alcohol products. Auxiliary cleavage (transesterification or reduction) yields enantiomerically enriched products with up to 96 % ee.

摘要

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通过串联 Wittig 重排/Mannich 反应序列实现了高对映选择性的α-烷基-α-羟基-β-氨基酯的合成。N-苄基或 N-Boc 亚胺的转化对于形成顺式氨基醇衍生物具有高选择性，而 N-Boc-2-(苯磺酰基)胺则生成反式氨基醇产物。辅助裂解（酯交换或还原）得到对映体富集产物，ee 值高达 96%。