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Copper‐Catalyzed Coupling of Oxime Acetates with Sodium Sulfinates: An Efficient Synthesis of Sulfone Derivatives
Author(s) -
Tang Xiaodong,
Huang Liangbin,
Xu Yanli,
Yang Jidan,
Wu Wanqing,
Jiang Huanfeng
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201311217
Subject(s) - chemistry , oxime , catalysis , bond cleavage , sulfone , phenacyl , oxidative coupling of methane , organic chemistry , dehydrogenation , combinatorial chemistry , alkylation , medicinal chemistry
Abstract Sulfone derivatives are important synthetic intermediates. However, the general method for their preparation is through traditional coupling reaction: the alkylation of sodium sulfinates with phenacyl halides. Based on our previous work on sodium sulfinates and oxime acetates, we herein report a novel method for sulfone derivatives by oxidative coupling with sodium sulfinates and oxime acetates using copper as catalyst. The sulfonylvinylamine products could be formed in excellent yields. Upon hydrolysis by silica gel in CH 2 Cl 2 , β‐ketosulfones could also be efficiently constructed. Various sulfonylvinylamines and β‐ketosulfones were obtained in good to excellent yields under the optimized reaction conditions. Mechanistic studies indicated that this transformation involved copper‐catalyzed NO bond cleavage, activation of a vinyl sp 2 CH bond, and CS bond formation. The oxime acetates act as both a substrate and an oxidant, thus the reaction needs no additional oxidants or additives.