Xing Shuya, Ma Cheng, Liu Wen, Ni Shao-Fei, Zhu Dianhu, Xu Li-Wen, Shao Xinxin
College of Material, Chemistry and Chemical Engineering, Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 311121, Zhejiang, P. R. China.
Department of Chemistry and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guang-dong Province, Shantou University, Shantou 515063, People's Republic of China.
Org Lett. 2023 Feb 24;25(7):1066-1071. doi: 10.1021/acs.orglett.2c04243. Epub 2023 Feb 13.
A novel strategy is demonstrated for Lewis base-activated trifluoromethylsulfinylation of allylic alcohols. Controllable synthesis of structurally varied allylic trifluoromethanesulfones via sigmatropic rearrangements was performed, and trifluoromethanesulfinate esters were achieved. This metal-free, catalytic divergent transformation features good functional group tolerance and late-stage modification of bioactive molecules. Mechanistic studies suggested that Lewis bases interact with -(trifluoromethylsulfinyl)phthalimide to generate an ion pair adduct followed by O-trifluoromethylsulfinylation with allylic alcohols.
展示了一种用于烯丙醇的路易斯碱活化三氟甲基亚磺酰化的新策略。通过[3,3] - 迁移重排实现了结构多样的烯丙基三氟甲磺酸酯的可控合成，并得到了三氟甲亚磺酸酯。这种无金属的催化发散转化具有良好的官能团耐受性和生物活性分子的后期修饰性。机理研究表明，路易斯碱与N - （三氟甲基亚磺酰基）邻苯二甲酰亚胺相互作用生成离子对加合物，随后与烯丙醇进行O - 三氟甲基亚磺酰化反应。
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