1,3-Dehydro-o-carborane: generation and reaction with arenes.
1,3-Dehydro-o-carborane: generation and reaction with arenes.
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DOI：
10.1002/anie.201405023
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发表时间：
2014-08
影响因子：
--
通讯作者：
Da Zhao;Jiji Zhang;Zuowei Xie
中科院分区：
文献类型：
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作者：
Da Zhao;Jiji Zhang;Zuowei Xie
像在现代芳烃化学中几十年来见证的苯炔的重要性一样，在过去的20年中，苯炔的三维相对物1，2-脱氢-O-碳硼烷（O-碳硼烷）已被用作合成子用于产生广泛的笼状碳官能化碳硼烷。然而，笼的选择性B官能化仍然是一项具有挑战性的任务。本文公开了1，3-脱氢-邻-碳硼烷的第一个实例，其特征在于具有多个键合特征的笼状C-B键，并且通过用非亲核碱处理3-重氮鎓-邻-碳硼烷四氟硼酸盐成功地产生。这提出了一种同时官能化笼状碳和硼顶点的新方法。
Like the importance of benzyne, witnessed in modern arene chemistry for decades, 1,2-dehydro-o-carborane (o-carboryne), a three-dimensional relative of benzyne, has been used as a synthon for generating a wide range of cage, carbon-functionalized carboranes over the past 20 years. However, the selective B functionalization of the cage still represents a challenging task. Disclosed herein is the first example of 1,3-dehydro-o-carborane featuring a cage C-B bond having multiple bonding characters, and is successfully generated by treatment of 3-diazonium-o-carborane tetrafluoroborate with non-nucleophilic bases. This presents a new methodology for simultaneous functionalization of both cage carbon and boron vertices.