用叔丁氧基硫代羰基进行胺保护/α-活化：在氮杂环丁烷锂化-亲电取代反应中的应用

Amine protection/α-activation with the tert-butoxythiocarbonyl group: application to azetidine lithiation-electrophilic substitution.

作者信息

Hodgson David M, Mortimer Claire L, McKenna Jeffrey M

机构信息

Department of Chemistry, Chemistry Research Laboratory, University of Oxford , Mansfield Road, Oxford OX1 3TA, U.K.

出版信息

Org Lett. 2015 Jan 16;17(2):330-3. doi: 10.1021/ol503441d. Epub 2014 Dec 23.

DOI:10.1021/ol503441d

PMID:25535850

Abstract

tert-Butoxythiocarbonyl (Botc), the long-neglected thiocarbonyl analogue of Boc, facilitates (unlike its alkoxycarbonyl cousin) α-lithiation and electrophile incorporation on N-Botc-azetidine. N,N,N',N'-endo,endo-Tetramethyl-2,5-diaminonorbornane proved optimal as a chiral ligand, generating adducts with er up to 92:8. Facile deprotection, under conditions that left the corresponding N-Boc systems intact, was achieved using either TFA or via thermolysis in ethanol.

摘要

叔丁氧基硫代羰基（Botc），长期被忽视的Boc硫代羰基类似物，（与它的烷氧基羰基同类物不同）促进了N-Botc-氮杂环丁烷上的α-锂化和亲电试剂引入。N,N,N',N'-内型,内型-四甲基-2,5-二氨基降冰片烷被证明是最佳的手性配体，生成的加合物对映体过量比高达92:8。使用三氟乙酸（TFA）或通过在乙醇中热解，在使相应的N-Boc体系保持完整的条件下实现了简便的脱保护。