Copper-Catalyzed Coupling of Oxime Acetates with Sodium Sulfinates: An Efficient Synthesis of Sulfone Derivatives
Copper-Catalyzed Coupling of Oxime Acetates with Sodium Sulfinates: An Efficient Synthesis of Sulfone Derivatives
复制标题
铜催化肟乙酸酯与亚磺酸钠的偶联：高效合成砜衍生物
DOI：
10.1002/anie.201311217
复制
发表时间：
2014-04-14
影响因子：
16.6
通讯作者：
Jiang, Huanfeng
中科院分区：
文献类型：
--
作者：
Tang, Xiaodong;Huang, Liangbin;Jiang, Huanfeng
砜衍生物是重要的合成中间体。然而，它们的制备方法一般是通过传统的偶联反应：亚硫酸钠与phenacyl卤化物的烷基化反应。在前人研究亚硫酸钠和乙酸肟酸盐的基础上，本文报道了一种以铜为催化剂，亚硫酸钠和乙酸肟酸盐氧化偶联合成砜衍生物的新方法。该磺胺基乙烯胺产品产率高。硅胶在CH2Cl2中水解后，也可以高效地构建-酮砜。在优化后的反应条件下，以优异的收率得到了多种磺酰基乙烯胺和-酮砜。机理研究表明，这种转化包括铜催化的NO键裂解、乙烯基sp(2) CH键的活化和CS键的形成。醋酸肟酸酯既作为底物又作为氧化剂，因此该反应不需要额外的氧化剂或添加剂。
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, -ketosulfones could also be efficiently constructed. Various sulfonylvinylamines and -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.