Copper-Catalyzed Coupling of Oxime Acetates with Sodium Sulfinates: An Efficient Synthesis of Sulfone Derivatives

• Published in: Angewandte Chemie International Edition 2014-04, Vol.53 (16), p.4205-4208
• Main Authors: Tang, Xiaodong, Huang, Liangbin, Xu, Yanli, Yang, Jidan, Wu, Wanqing, Jiang, Huanfeng
• Format: Article
• Language: English
• Subjects: Acetates; Bonding; cleavage reactions; Copper; CH activation; Derivatives; Joining; Oxidants; Oxidizing agents; Oximes; Sodium; sulfone derivatives; Sulfones
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201311217

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 CH2Cl2, 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 NO bond cleavage, activation of a vinyl sp2 CH bond, and CS bond formation. The oxime acetates act as both a substrate and an oxidant, thus the reaction needs no additional oxidants or additives. Copper brings us together: The title reaction involves copper‐catalyzed NO bond cleavage, activation of a vinyl sp2 CH bond and CS bond formation; it uses simple oxime acetates and sodium sulfinates to synthesize sulfonylvinylamine products without the need for additional oxidants or additives. Upon hydrolysis, useful β‐ketosulfones are obtained.