Heteroarene Phosphinylalkylation via a Catalytic, Polarity-Reversing Radical Cascade
Heteroarene Phosphinylalkylation via a Catalytic, Polarity-Reversing Radical Cascade
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DOI：
10.1021/acscatal.9b01580
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发表时间：
2019-06-01
期刊：
影响因子：
12.9
通讯作者：
Nagib, David A.
中科院分区：
文献类型：
--
作者：
Buquoi, J. Quentin;Lear, Jeremy M.;Nagib, David A.
发展了一种极性反转自由基级联反应策略，通过邻位C-C键和C-P键的形成实现烯烃双官能化。通过光催化产生亲电P中心自由基，能够实现这种同时添加磷和杂芳烃穿过烯烃的方法。在与烯烃的化学选择性加成后，所得的亲核C-中心自由基选择性地与亲电杂芳烃如吡啶结合。这种用于膦基烷基化的多组分偶联方案补充了用于烯烃的氢化膦基化和芳烃的C-H膦基化的经典双组分方法。包括竞争和光猝灭实验提供了深入了解这种极性反转途径的选择性和机制。
A polarity-reversing radical cascade strategy for alkene difunctionalization by vicinal C-C and C-P bond formation has been developed. This approach to concurrently adding phosphorus and a heteroarene across an olefin is enabled by photocatalytic generation of electrophilic P-centered radicals. Upon chemoselective addition to an olefin, the resulting nucleophilic C-centered radical selectively combines with electrophilic heteroarenes, such as pyridines. This multicomponent coupling scheme for phosphinylalkylation complements classic two-component methods for hydrophosphinylation of alkenes and C-H phosphinylation of arenes. Included competition and photoquenching experiments provide insight into the selectivity and mechanism of this polarity-reversal pathway.