Long-Range C-H Bond Activation by RhIII-Carboxylates
Long-Range C-H Bond Activation by RhIII-Carboxylates
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DOI：
10.1021/ja508367m
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发表时间：
2014-10-22
影响因子：
15
通讯作者：
Gunnoe, T. Brent
中科院分区：
文献类型：
--
作者：
O'Reilly, Matthew E.;Fu, Ross;Gunnoe, T. Brent
通过协同金属化-去质子化（CMD）机制的传统C-H键活化涉及C-H键的预配位，随后从内部碱去质子化。本文报道的是距离Rh-III离子6个键的未配位的苄基C-H键的“通过芳烃”活化。的机制，这是通过实验和DFT研究进行了研究，通过脱芳构化的二甲苯中间体。在加入吡啶碱以提供热力学陷阱时，通过光谱观察到该中间体。
Traditional C-H bond activation by a concerted metalation-deprotonation (CMD) mechanism involves precoordination of the C-H bond followed by deprotonation from an internal base. Reported herein is a "through-arene" activation of an uncoordinated benzylic C-H bond that is 6 bonds away from a Rh-III ion. The mechanism, which was investigated by experimental and DFT studies, proceeds through a dearomatized xylene intermediate. This intermediate was observed spectroscopically upon addition of a pyridine base to provide a thermodynamic trap.