P(NMe2)3-Mediated Umpolung Alkylation and Nonylidic Olefination of α-Keto Esters.
P(NMe2)3-Mediated Umpolung Alkylation and Nonylidic Olefination of α-Keto Esters.
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DOI：
10.1021/acs.orglett.5b01784
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发表时间：
2015-08-07
期刊：
影响因子：
5.2
通讯作者：
Radosevich AT
中科院分区：
文献类型：
--
作者：
Wang SR;Radosevich AT
商业磷基试剂 (P-(NMe2)3) 介导芳酰甲酸甲酯与苄基和烯丙基溴化物的反极性烷基化，在后处理时产生巴比尔型加成或无叶立德烯化产物。该反应序列由三配位磷试剂与 α-酮酯化合物的双电子氧化还原加成引发（Kukhtin-Ramirez 加成）。为化学选择性提供了机械原理，这是非金属介导的 C-C 键形成策略成功的基础。
A commercial phosphorus-based reagent (P-(NMe2)3) mediates umpolung alkylation of methyl aroylformates with benzylic and allylic bromides, leading to either Barbier-type addition or ylide-free olefination products upon workup. The reaction sequence is initiated by a two-electron redox addition of the tricoordinate phosphorus reagent with an α-keto ester compound (Kukhtin–Ramirez addition). A mechanistic rationale is offered for the chemoselectivity upon which the success of this nonmetal mediated C–C bond forming strategy is based.