The visible-light-induced cobalt-catalyzed hydrogen evolution radical coupling reaction has emerged as a powerful strategy for the synthesis of structurally diverse compounds, whereas transformations with phosphorus-centered radicals remain largely unexplored. Herein, a photoinduced allylic radical phosphinylation of alkenes with secondary phosphine oxides by cobaloxime catalysis is described. The reaction tolerates a wide range of alkenes, including activated electron-deficient alkenes and nonactivated aryl- and alkylsubstituted alkenes, affording allylic phosphine oxides in good yields with high site-selectivities. Furthermore, this photoinduced cobaloxime catalytic system can be extended to the radical diphosphinylation of simple alkenes to construct DPPP-dioxide analogues. The new phosphine–olefin and diphosphine ligands are generated smoothly by reduction of mono- and diphosphinylation products.

中文翻译：

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光诱导钴肟催化烯烃烯丙基单和二膦酰化反应与析氢


可见光诱导的钴催化析氢自由基偶联反应已成为合成结构多样化合物的强大策略，而与磷中心自由基的转化在很大程度上仍未得到探索。在此，描述了通过钴肟催化光诱导烯烃与仲膦氧化物的烯丙基自由基化。该反应可耐受多种烯烃，包括活化的缺电子烯烃和非活化的芳基和烷基取代烯烃，从而获得烯丙基膦氧化物，产率高，位点选择性高。此外，这种光诱导钴肟催化系统可以扩展到简单烯烃的自由基二膦酰化，以构建 DPPP-二氧化类似物。新的膦-烯烃和二膦配体是通过还原单膦和二膦酰化产物而顺利生成的。