Nickel-Catalyzed Reaction between Vinyl Azides and an Alkyl Sulfonyl Radical Generated from DMSO: Rapid Access to β-Keto Sulfones

Abstract

A sustainable method for the construction of valuable β-keto sulfones lies in the reaction between vinyl azides and the alkyl sulfonyl radical generated from the low-cost and comparatively steady bulk chemical dimethyl sulfoxide (DMSO) that has been developed. This strategy features mild and economical reaction conditions using inexpensive NiCl 2 as the catalyst and H 2 O 2 as the green oxidant. The conversion occurs through a sequence of ordered processes consisting of a sulfonyl radical addition, denitrogen, hydrogen abstraction, and hydrolysis. Mechanistic studies indicate that sulfinic acid produced from DMSO plays an essential role in the reduction of Ni(III). The sensitivity assessment and gram-scale experiments proceed smoothly to demonstrate the robustness and practicality of this protocol.

Lead-free perovskite Cs3Bi2Br9/TiO2 composites for atmospheric photocatalytic oxidation of sulfides

“…11 Hence, the rational control of reactive species derived from photogenerated electrons and holes is an essential prerequisite for highly selective oxidation reactions. To address these obstacles, a porous carbazolic conjugated microporous polymer (C-CMP), 12 core–shell TiO 2 @polydopamine, 13 and an ultrathin uranyl-organic framework nanosheet material 14 were designed as photocatalysts to induce the oxidation of sulfides, 15 and a series of sulfoxides were synthesized in high yields. 16 However, these methods depend on photocatalysts that are hard to obtain and environmentally detrimental, and the photocatalytic activities of these photocatalysts remain low, even when using an additional oxidant (O 2 or other oxidants), sacrificial reagent, co-catalyst or redox mediator, which severely restricts their large-scale applications in the synthetic field.…”