通过烯酸的氨腈化合成阿马噻林酰胺。

Synthesis of Amathaspiramides by Aminocyanation of Enoates.

机构信息

Department of Chemistry, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL (USA).

Merck Discovery Chemistry, 2000 Galloping Hill Road, Kenilworth, NJ 07033 (USA).

出版信息

Angew Chem Int Ed Engl. 2015 Aug 17;54(34):9963-6. doi: 10.1002/anie.201503982. Epub 2015 Jun 30.

DOI:10.1002/anie.201503982

PMID:26130161

Abstract

Concise routes for the total and formal syntheses of the amathaspiramides were developed through a formal [3+2] cycloaddition between lithium(trimethylsilyl)diazomethane and α,β-unsaturated esters. The effectiveness of this new cycloaddition for the construction of Δ(2)-pyrazolines containing a α-tert-alkylamino carbon center and subsequent facile protonolytic N-N bond cleavage allows the synthesis of a key intermediate of the amathaspiramides and other α,α-disubstituted amino acid derivatives.

摘要

通过锂（三甲基硅基）重氮甲烷和α,β-不饱和酯之间的[3+2]环加成反应，开发了总合成和正规合成 amataspiramides 的简洁路线。这种新的环加成反应对于构建含有α-叔烷基氨基碳中心的Δ(2)-吡唑啉以及随后容易发生质子裂解的 N-N 键的有效性，使得 amataspiramides 和其他α,α-二取代氨基酸衍生物的关键中间体的合成成为可能。