环氧化合物介导的 α-氨基酸衍生的叔烯丙基、炔丙基和苄基胺的 Stevens 重排：方便获得多取代吗啉-2-酮。

Epoxide-Mediated Stevens Rearrangements of α-Amino-Acid-Derived Tertiary Allylic, Propargylic, and Benzylic Amines: Convenient Access to Polysubstituted Morpholin-2-ones.

机构信息

Hefei National Laboratory for Physical Sciences at the Microscale, Center for Excellence in Molecular Synthesis, and Department of Chemistry, University of Science and Technology of China, Hefei, Anhui, 230026, China.

Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032, China.

出版信息

Chemistry. 2019 Apr 5;25(20):5169-5172. doi: 10.1002/chem.201900635. Epub 2019 Mar 21.

DOI:10.1002/chem.201900635

PMID:30896074

Abstract

A new strategy has been established for the synthesis of polysubstituted morpholin-2-ones through Stevens rearrangements of tertiary amines via in situ activation with epoxides. A range of α-amino acid-derived tertiary allylic, propargylic, and benzylic amines reacted with epoxides in the presence of zinc halide catalysts to afford structurally diverse allyl-, allenyl-, and benzyl-substituted morpholin-2-ones, respectively, in moderate-to-good yields with high regioselectivity. The process involves [2,3]- and [1,2]-Stevens rearrangements of quaternary ammonium ylide intermediates and constitutes a very convenient method to prepare polysubstituted morpholin-2-ones through tandem formation of C-N, C-O, and C-C bonds. Moreover, replacing epoxides with aziridines permitted the synthesis of polysubstituted piperazin-2-ones.

摘要

通过环氧乙烷原位活化，建立了一种通过斯特凡斯重排合成多取代吗啉-2-酮的新策略。一系列α-氨基酸衍生的叔烯丙基、炔丙基和苄基胺在卤化锌催化剂存在下与环氧化物反应，分别以中等至良好的收率和高区域选择性得到结构多样的烯丙基、烯丙基和苄基取代的吗啉-2-酮。该过程涉及季铵叶立德中间体的[2,3]-和[1,2]-斯特凡斯重排，构成了通过 C-N、C-O 和 C-C 键的串联形成来制备多取代吗啉-2-酮的非常方便的方法。此外，用氮丙啶取代环氧化物可以合成多取代哌嗪-2-酮。