Hydro-phosphorothiolation of Styrene and Cyclopropane with <i>S</i>‑Hydrogen Phosphorothioates under Ambient Conditions

A metal-free hexafluoroisopropanol-mediated hydro-phosphorothiolation of styrenes and donor–acceptor cyclopropanes with S-hydrogen phosphorothioates in a Markovnikov fashion has been developed under ambient reaction conditions to afford a library of S-alkyl phosphorothioates. Notably, this strategy provides a simple and efficient way to produce biologically significant kitazin and iprobenfos derivatives. Mechanistic studies disclose that the reaction proceeds through a carbocation intermediate.本研究开发了一种无金属、六氟异丙醇（hexafluoroisopropanol）介导的马氏选择性氢膦硫代化反应，可在常温反应条件下，使苯乙烯类化合物、供体-受体环丙烷与S-氢硫代磷酸酯发生反应，从而构建S-烷基硫代磷酸酯类化合物文库。值得注意的是，该策略为制备具有重要生物活性的克瘟散（kitazin）与丙硫磷（iprobenfos）衍生物提供了简便高效的途径。机理研究揭示，该反应经由碳正离子中间体完成。