Photocatalyst‐Free Visible Light‐Induced Synthesis of β‐Oxo Sulfones via Oxysulfonylation of Alkenes with Arylazo Sulfones and Dioxygen in Air

Abstract

A catalyst‐free strategy has been established for the synthesis of β‐oxo sulfones via visible light‐induced oxysulfonylation of alkenes with arylazo sulfones with dioxygen in air. The present photoinduced transformation proceeds smoothly at room temperature in the absence of an external photosensitizer, which not only provides a mild and efficient approach to various β‐oxo sulfones, but also opens a different reaction mode for the photochemical reaction of arylazo sulfones.magnified image

Advances in Oxosulfonylation Reaction

“…In 2019, Wei group [63] introduced a photocatalyst‐free, visible light (blue light) induced oxosulfonylation of alkenes 22a with arylazo sulfones 22b in 1,4‐dioxane/H 2 O (2:1) solvent using aerial oxygen as an oxidant. The desired β ‐ketosulfones 22c were formed in 34–80% yields after 16 to 24 h at room temperature (Scheme 22).…”

“…In light of its extensive efficacies, numerous protocols of oxosulfonylation such as metal-catalyzed oxosulfonylation, [46][47][48][49][50][51][52][53][54][55] organophotocatalyzed oxosulfonylation, [32,[56][57][58] metal-based photocatalyzed oxosulfonylation, [59][60][61] catalyst free photo-induced oxosulfonylation [62][63][64] etc have been developed. Very recently, oxygen triggered oxosulfonylation methods [65][66][67][68][69][70][71][72] show great interest among synthetic organic chemists.…”

Pyridine‐Catalysed Desulfonylative Addition of β‐Diketones to Arylazosulfones via Diaziridine Rearrangement

“…Arylazosulfones, which are important building blocks, [6] were widely applied as aryl, [7] arylamine, [8] or sulfone sources [9a] via chemical bond (C−N, N−N, and N−S) cleavage under different conditions (Scheme 1a–1c). On the other hand, arylazosulfones also have been demonstrated as versatile radical partners in photochemical coupling reactions due to their good photochemical behaviors for constructing various organic molecules [9] .…”

Recent Advances in Arylations and Sulfonylations of Arylazo Sulfones

“…同时, β-羰基砜也是一 种重要的有机合成中间体, 可用来合成 4H-吡喃、酮类、 石松碱、取代炔烃、丙二烯手性烯砜、喹啉衍生物以及 具有光化学活性的 β-羟基砜等重要有机化合物 [32] . 2019 年, 魏伟课题组 [33] 开发了一种利用可见光诱导下烯烃 与芳基偶氮砜和氧气的氧砜反应构建 β-羰基砜化合物 随后, 魏伟课题组 [34] 又利用可见光诱导下芳基偶 氮砜与炔烃和氧气反应实现了一系列 β-羰基砜的构建. 烯基砜化合物是一类重要的有机物结构单元, 广泛 存在于各类具有抗癌活性的天然产物、药物分子和医药 中间体中.…”