使用α-苯基乙烯基锍盐合成六元及七元氮杂环化合物。

Synthesis of 6- and 7-Membered N-Heterocycles Using α-Phenylvinylsulfonium Salts.

作者信息

Matlock Johnathan V, Svejstrup Thomas D, Songara Pradip, Overington Sarah, McGarrigle Eoghan M, Aggarwal Varinder K

机构信息

School of Chemistry, University of Bristol , Cantock's Close, BS8 1TS, Bristol, U.K.

Centre for Synthesis and Chemical Biology, UCD School of Chemistry, University College Dublin , Belfield, Dublin 4, Ireland.

出版信息

Org Lett. 2015 Oct 16;17(20):5044-7. doi: 10.1021/acs.orglett.5b02516. Epub 2015 Sep 30.

DOI:10.1021/acs.orglett.5b02516

PMID:26421884

Abstract

A concise synthesis of stereodefined C-substituted morpholines, piperazines, azepines, and oxazepines in moderate to excellent yields (27% to 75%) is reported by reaction of 1,2- or 1,3-amino alcohol/1,2- or 1,3-diamine with an α-phenylvinylsulfonium salt. High levels of regio- and diastereoselectivity (from 2:1 to >20:1) are observed through judicious choice of base (Cs2CO3) and solvent (CH2Cl2). Reactions are performed at ambient temperature and open to air and do not require anhydrous solvent. The deprotection of the N-sulfonamide protecting groups (N-Ts and N-Ns) is also demonstrated. Factors affecting regio- and diastereocontrol are discussed.

摘要

据报道，通过1,2-或1,3-氨基醇/1,2-或1,3-二胺与α-苯基乙烯基锍盐反应，能以中等至优异的产率（27%至75%）简洁合成立体定向的C-取代吗啉、哌嗪、氮杂卓和氧杂卓。通过明智地选择碱（碳酸铯）和溶剂（二氯甲烷），可观察到高水平的区域选择性和非对映选择性（从2:1至>20:1）。反应在室温下进行，可在空气中操作，且不需要无水溶剂。还展示了N-磺酰胺保护基（N-对甲苯磺酰基和N-对硝基苯磺酰基）的脱保护。讨论了影响区域和非对映控制的因素。