卤代乙烯和芳基碘化物的甲酸介导还原交叉偶联：通过钯（I）催化的α-取代反应
Formate-Mediated Reductive Cross-Coupling of Vinyl Halides and Aryl Iodides: -Substitution via Palladium(I) Catalysis.
作者信息
Santana Catherine G, Teoh Yhin Sarah, Evarts Madeline M, Shezaf Jonathan Z, Krische Michael J
机构信息
Department of Chemistry, University of Texas at Austin, Austin, Texas 78712, United States.
出版信息
Org Lett. 2024 Aug 23;26(33):7055-7059. doi: 10.1021/acs.orglett.4c02642. Epub 2024 Aug 12.
Abstract
Formate-mediated reductive cross-couplings of vinyl halides with aryl iodides via palladium(I) catalysis occur with highly uncommon -substitution. The active dianionic palladium(I) catalyst, [PdI][NBu], is generated from Pd(OAc), BuNI, and formate. Oxidative addition of aryl iodide followed by dissociation of the dimer provides the monomeric anionic T-shaped arylpalladium(II) species, [Pd(Ar)(I)(NBu)], which, upon vinyl halide carbopalladation, forms products of -substitution by way of palladium(IV) carbenes, as corroborated by deuterium-labeling experiments.
摘要
通过钯（I）催化实现的卤代乙烯与芳基碘化物的甲酸酯介导的还原交叉偶联反应以极不常见的β-取代方式发生。活性双阴离子钯（I）催化剂[PdI][NBu]由Pd(OAc)₂、Bu₃NI和甲酸酯生成。芳基碘化物的氧化加成随后二聚体的解离产生单体阴离子T形芳基钯（II）物种[Pd(Ar)(I)(NBu)]，在卤代乙烯碳钯化后，通过钯（IV）卡宾形成β-取代产物，氘标记实验证实了这一点。
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