As the “chemical chameleon”, sulfonyl-containing compounds and their variants have been merged with various types of reactions for the efficient construction of diverse molecular architectures by taking advantage of their incredible reactive flexibility. Currently, their involvement in radical transformations, in which the sulfonyl group typically acts as a leaving group via selective C–S, N–S, O–S, S–S, and Se–S bond cleavage/functionalization, has facilitated new bond formation strategies which are complementary to classical two-electron cross-couplings via organometallic or ionic intermediates. Considering the great influence and synthetic potential of these novel avenues, we summarize recent advances in this rapidly expanding area by discussing the reaction designs, substrate scopes, mechanistic studies, and their limitations, outlining the state-of-the-art processes involved in radical-mediated desulfonylation and related transformations. With a specific emphasis on their synthetic applications, we believe this review will be useful for medicinal and synthetic organic chemists who are interested in radical chemistry and radical-mediated desulfonylation in particular.

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通过自由基过程脱磺酰基：有机合成的最新进展

作为“化学变色龙”，含磺酰基化合物及其变体已与各种类型的反应相结合，利用其令人难以置信的反应灵活性，有效地构建不同的分子结构。目前，它们参与自由基转化，其中磺酰基通常通过选择性 C-S、N-S、O-S、S-S 和 Se-S 键断裂/官能化作为离去基团，促进了新键通过有机金属或离子中间体与经典的双电子交叉偶联互补的形成策略。考虑到这些新途径的巨大影响和合成潜力，我们通过讨论反应设计、底物范围、机理研究及其局限性，总结了这一快速发展领域的最新进展，概述了涉及自由基介导的脱磺酰化和相关转化的最新工艺。特别强调它们的合成应用，我们相信这篇综述将对那些对自由基化学特别是自由基介导的脱磺酰化感兴趣的药物和合成有机化学家有用。