Boron-Mediated Carbon-Carbon Bond Cleavage and Rearrangement of Benzene Forming the Borepinyl Radical and Borole Derivatives,Journal of the American Chemical Society

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Boron-Mediated Carbon-Carbon Bond Cleavage and Rearrangement of Benzene Forming the Borepinyl Radical and Borole Derivatives
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-05-08 , DOI: 10.1021/jacs.0c02131
Jiwen Jian ₁ , Xuan Wu ₂ , Mohua Chen ₂ , Mingfei Zhou ₂

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The reaction of atomic boron with benzene in solid neon has been investigated by matrix isolation infrared spectroscopy with isotopic substitutions as well as quantum chemical calculations. The reaction is initiated by boron atom addition to benzene in forming an η2-(1, 4) Π adduct (A). A borepinyl radical (B) formed by C-C bond insertion is also observed on annealing. The η2-(1,4) Π adduct photo-isomerizes to an unprecedented borole substituted vinyl radical intermediate (C) via ring opening and rearrangement reactions, which involves an antiaromatic borole subunit. A previously unconsidered 1-ethynyl-2-dihydro-1H-borole radical (D) is generated as the final product under UV light irradiation. The results presented herein give new insight into the benzene carbon-carbon bond cleavage and rearrangement reactions mediated by a nonmetal and provide a possible route for the construction of hetero-cyclic borepinyl and borole species via benzene ring opening and rearrangement reactions.

中文翻译：

硼介导的碳-碳键裂解和苯重排形成硼烷基和硼衍生物

已经通过具有同位素取代的基质隔离红外光谱以及量子化学计算研究了原子硼与苯在固体氖中的反应。该反应由硼原子加成到苯引发，形成 η2-(1, 4) Π 加合物 (A)。在退火时还观察到由 CC 键插入形成的空心基自由基 (B)。η2-(1,4) Π 加合物通过开环和重排反应光异构化为前所未有的硼取代的乙烯基自由基中间体 (C)，其中涉及反芳香族硼酸亚基。在紫外光照射下，生成了以前未考虑的 1-ethynyl-2-dihydro-1H-borole 自由基 (D) 作为最终产物。

更新日期：2020-05-08

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