Organophosphorus-Catalyzed Deoxygenation of Sulfonyl Chlorides: Electrophilic (Fluoroalkyl)sulfenylation by PIII/PV=O Redox Cycling
Organophosphorus-Catalyzed Deoxygenation of Sulfonyl Chlorides: Electrophilic (Fluoroalkyl)sulfenylation by PIII/PV=O Redox Cycling
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DOI：
10.1002/anie.201813919
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发表时间：
2019-02-25
影响因子：
16.6
通讯作者：
Radosevich, Alexander T.
中科院分区：
文献类型：
--
作者：
Ghosh, Avipsa;Lecomte, Morgan;Radosevich, Alexander T.
报道了一种由磺酰氯为原料，有机磷催化脱氧氧原子转移进行亲电亚磺酰化反应的方法。该C-S键形成反应由容易获得的小环膦（磷杂环丁烷）与氢硅烷末端还原剂结合催化，以提供对硫基亲电体的一般进入，包括有价值的三氟甲基、全氟烷基和杂芳基衍生物，这些衍生物以其他方式难以获得。机制研究表明，通过干预的关闭周期静息状态硫代膦离子的磺酰基底物的双重脱氧收益。该催化方法代表了使用稳定的氧化膦作为预催化剂的操作简单的协议，并表现出广泛的官能团耐受性。
A method for electrophilic sulfenylation by organophosphorus-catalyzed deoxygenative O-atom transfer from sulfonyl chlorides is reported. This C-S bond-forming reaction is catalyzed by a readily available small-ring phosphine (phosphetane) in conjunction with a hydrosilane terminal reductant to afford a general entry to sulfenyl electrophiles, including valuable trifluoromethyl, perfluoroalkyl, and heteroaryl derivatives that are otherwise difficult to access. Mechanistic investigations indicate that the twofold deoxygenation of the sulfonyl substrate proceeds by the intervention of an off-cycle resting state thiophosphonium ion. The catalytic method represents an operationally simple protocol using a stable phosphine oxide as a precatalyst and exhibits broad functional-group tolerance.