Chu Xue-Qiang, Ge Danhua, Cui Yan-Ying, Shen Zhi-Liang, Li Chao-Jun
Institute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, China.
Department of Chemistry and FQRNT Centre for Green Chemistry and Catalysis, McGill University, Montreal, Quebec H3A 0B8, Canada.
Chem Rev. 2021 Oct 27;121(20):12548-12680. doi: 10.1021/acs.chemrev.1c00084. Epub 2021 Aug 13.
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.
作为“化学变色龙”，含磺酰基的化合物及其变体通过利用其令人难以置信的反应灵活性，已与各种类型的反应相结合，用于高效构建多样的分子结构。目前，它们参与自由基转化，其中磺酰基通常通过选择性的C-S、N-S、O-S、S-S和Se-S键裂解/官能化作为离去基团，促进了新的键形成策略，这些策略与通过有机金属或离子中间体进行的经典双电子交叉偶联互补。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，总结了这个迅速发展领域的最新进展，概述了自由基介导的脱磺酰化及相关转化所涉及的前沿方法。特别强调它们的合成应用，我们相信这篇综述对于对自由基化学尤其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将是有用的。
