通过N-叔丁基苯基氮杂环丙烷的区域和立体特异性锂化反应合成光学活性芳基氮杂环丙烷。

Synthesis of optically active arylaziridines by regio- and stereospecific lithiation of N-bus-phenylaziridine.

作者信息

Musio Biagia, Clarkson Guy J, Shipman Michael, Florio Saverio, Luisi Renzo

机构信息

Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry CV4 7AL, UK.

出版信息

Org Lett. 2009 Jan 15;11(2):325-8. doi: 10.1021/ol802487v.

DOI:10.1021/ol802487v

PMID:19086905

Abstract

Alpha,alpha-disubstituted aziridines can be produced in good yields by selective lithiation of N-tert-butylsulfonyl-2-phenylaziridine (n-BuLi/TMEDA, Et(2)O) at the benzylic position and subsequent trapping with a range of electrophiles. Repetition of the lithiation/electrophilic trapping sequence provides a stereocontrolled route to trisubstituted aziridines. Using (R)-N-tert-butylsulfonyl-2-phenylaziridine, the alpha,alpha-disubstituted aziridines can be produced as single enantiomers (er >98:2), indicating that the intermediate organolithium is configurationally stable. Efficient aziridine ring-opening reactions leading to 1,2-diamines and 1,4-diamines are also reported.

摘要

通过在苄基位置对N-叔丁基磺酰基-2-苯基氮丙啶（正丁基锂/四甲基乙二胺，乙醚）进行选择性锂化，随后用一系列亲电试剂捕获，可以高产率制备α,α-二取代氮丙啶。重复锂化/亲电捕获序列可提供一条立体控制的路线来合成三取代氮丙啶。使用(R)-N-叔丁基磺酰基-2-苯基氮丙啶，可以制备出单一对映体的α,α-二取代氮丙啶（对映体过量>98:2），这表明中间体有机锂在构型上是稳定的。还报道了高效的氮丙啶开环反应，生成1,2-二胺和1,4-二胺。