111895-33-1Relevant articles and documents
Heterogeneous copper-catalyzed oxidative coupling of oxime acetates with sodium sulfinates: An efficient and practical synthesis of β-keto sulfones
Xia, Jianhui,Huang, Xue,You, Shengyong,Cai, Mingzhong
, (2019/06/08)
An efficient and practical route to β-keto sulfones has been developed through heterogeneous oxidative coupling of oxime acetates with sodium sulfinates by using an MCM-41-supported Schiff base-pyridine bidentate copper (II) complex [MCM-41-Sb,Py-Cu (OAc)2] as the catalyst and oxime acetates as an internal oxidant, followed by hydrolysis. The reaction generates a variety of β-keto sulfones in good to excellent yields. This new heterogeneous copper (II) catalyst can be easily prepared via a simple procedure from readily available and inexpensive reagents and exhibits the same catalytic activity as Cu (OAc)2. MCM-41-Sb,Py-Cu (OAc)2 is also easy to recover and is recyclable up to eight times with almost consistent activity.
Unexpected Role of p-Toluenesulfonylmethyl Isocyanide as a Sulfonylating Agent in Reactions with α-Bromocarbonyl Compounds
Chen, Jiajia,Guo, Wei,Wang, Zhenrong,Hu, Lin,Chen, Fan,Xia, Yuanzhi
, p. 5504 - 5512 (2016/07/13)
The reactions of p-toluenesulfonylmethyl isocyanide (TosMIC) with α-bromocarbonyl compounds leading efficiently to α-sulfonated ketones, esters, and amides were reported, in which an explicit new role of TosMIC as the sulfonylating agent was uncovered for the first time. Mechanistic study by control experiments and DFT calculations suggested that the reaction is initiated by Cu(OTf)2-catalyzed hydration of TosMIC to form a formamide intermediate, which undergoes facile C-S bond cleavage under the mediation of a Cs2CO3 additive.
Copper-catalyzed coupling of oxime acetates with sodium sulfinates: An efficient synthesis of sulfone derivatives
Tang, Xiaodong,Huang, Liangbin,Xu, Yanli,Yang, Jidan,Wu, Wanqing,Jiang, Huanfeng
supporting information, p. 4205 - 4208 (2014/05/06)
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 2Cl2, 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.
