Anomalous reactivity of silylborane: transition-metal-free boryl substitution of aryl, alkenyl, and alkyl halides with silylborane/alkoxy base systems.
Anomalous reactivity of silylborane: transition-metal-free boryl substitution of aryl, alkenyl, and alkyl halides with silylborane/alkoxy base systems.
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DOI：
10.1021/ja309578k
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发表时间：
2012-11
影响因子：
15
通讯作者：
E. Yamamoto;Kiyotaka Izumi;Y. Horita;Hajime Ito
中科院分区：
文献类型：
--
作者：
E. Yamamoto;Kiyotaka Izumi;Y. Horita;Hajime Ito
已经观察到有机卤化物与甲硅烷基硼烷在烷氧基碱存在下的意外硼基化。这种形式上的亲核硼基取代可以应用于具有高官能团相容性的广泛底物。即使是空间位阻的芳基溴也能高产率地得到相应的硼基化合物。初步的机理研究表明，这种硼基取代既不是过渡金属污染，也不是自由基介导的过程。
An unexpected borylation of organic halides with a silyborane in the presence of an alkoxy base has been observed. This formal nucleophilic boryl substitution can be applied to a broad range of substrates with high functional group compatibility. Even sterically hindered aryl bromides afforded the corresponding boryl compounds in high yields. Preliminary mechanistic studies indicated that this boryl substitution is promoted by neither transition-metal contamination nor a radical-mediated process.