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

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 CH2 Cl2 , 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 sp(2) 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.

Catalyst‐Controlled Selectivity in C−S Bond Formation: Highly Efficient Synthesis of C2‐ and C3‐Sulfonylindoles

“…Subsequently,wealso investigated the reactionsmechanism. On the basis of our results (Scheme 1) and literature reports, [10] two plausible mechanisms are proposed. Initially,t he outcome of the Cu-catalyzedm echanism is illustrated (Scheme 2).…”

Recent advances in the synthesis of vinyl sulfones

“…39 Synthesis of vinyl sulfones from terminal epoxides and sodium sulfinates. activation of a vinyl sp2 C-H bond, and C-S bond formation for synthesis of β-sulfonylvinylamines from sodium sulfinates and oxime acetates was reported by Jiang and co-workers68 (Scheme 40). One proposed mechanism is might undergo the Cu II /Cu I catalytic cycle through a single electron transfer process.…”

Palladium‐Catalyzed Regio‐ and Stereoselective Sulfonylation of Aryl Propiolates with Sulfonyl Hydrazides: Access to (E)‐β‐Aryl Sulfonyl Acrylates

“…Examples about the cross-coupling of terminal alkynes with sulfinic acid, sulfinate salts or sulfonyl hydrazides have been reported. Based on our continuing interest in the formation and transformation of sulfonyl compounds, [16] herein, we develop the palladium(II)catalyzed regio-and stereoselective sulfonylation of aryl propiolates with sulfonyl, a novel and convenient strategy for the synthesis of (E)-β-aryl sulfonyl acrylates. [10,13c,14] In these reports about sulfonylation of terminal alkenes or aryl propiolic acids, (Z)-vinyl sulfones were usually the only products, due to the small steric resistance of disubstituted internal vinyl unit.…”