Merging Photoredox with 1,2-Metallate Rearrangements: The Photochemical Alkylation of Vinyl Boronate Complexes
Merging Photoredox with 1,2-Metallate Rearrangements: The Photochemical Alkylation of Vinyl Boronate Complexes
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DOI：
10.1021/jacs.7b02569
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发表时间：
2017-04-26
影响因子：
15
通讯作者：
Aggarwal, Varinder K.
中科院分区：
文献类型：
--
作者：
Silvi, Mattia;Sandford, Christopher;Aggarwal, Varinder K.
乙烯基硼酸盐在可见光下与缺电子的烷基碘化物反应生成硼酯，其中形成了两个新的碳-碳键。反应发生的方式是将缺电子的烷基自由基加到硼酸乙烯基上，然后与另一个碘化烷基分子进行电子转移，使链继续，并引发1,2-金属酸盐重排。在许多情况下，使用光氧化还原催化剂可显著提高产率。自由基前体的范围包括-碘酮、酯、腈、伯胺、-氟化卤代乙酸酯和全氟烷基碘化物。
Vinyl boronates react with electron-deficient alkyl iodides in the presence of visible light to give boronic esters in which two new C-C bonds have been created. The reaction occurs by radical addition of an electron-deficient alkyl radical to the vinyl boronate followed by electron transfer with another molecule of alkyl iodide, continuing the chain, and triggering a 1,2-metalate rearrangement. In a number of cases, the use of a photoredox catalyst enhances yields significantly. The scope of the radical precursor includes alpha-iodo ketones, esters, nitriles, primary amides, alpha-fluorinated halo-acetates and perfluoroalkyl iodides.