Cuprous Oxide Catalyzed Oxidative C-C Bond Cleavage for C-N Bond Formation: Synthesis of Cyclic Imides from Ketones and Amines.
Cuprous Oxide Catalyzed Oxidative C-C Bond Cleavage for C-N Bond Formation: Synthesis of Cyclic Imides from Ketones and Amines.
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DOI：
10.1002/anie.201508071
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发表时间：
2015-11
影响因子：
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通讯作者：
Min Wang;Jianmin Lu;Jiping Ma;Zhe Zhang;Feng Wang
中科院分区：
文献类型：
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作者：
Min Wang;Jianmin Lu;Jiping Ma;Zhe Zhang;Feng Wang
C-C 键的选择性氧化断裂提供了一种有机骨架功能化的简单方法。本文报道了在氧化亚铜催化剂上以分子氧作为氧化剂，酮的氧化性C-C键断裂形成C-N键。多种酮和胺可转化为环状酰亚胺，产率中等至优异。深入研究表明，与羰基相邻的α-C-H和β-C-H键对于C-C键的断裂都是不可或缺的。 DFT 计算表明反应是随着 α-C-H 键的氧化而引发的。胺降低C-C键断裂的活化能，从而促进反应。提出了对 C-C 键断裂机制的新见解。
Selective oxidative cleavage of a C-C bond offers a straightforward method to functionalize organic skeletons. Reported herein is the oxidative C-C bond cleavage of ketone for C-N bond formation over a cuprous oxide catalyst with molecular oxygen as the oxidant. A wide range of ketones and amines are converted into cyclic imides with moderate to excellent yields. In-depth studies show that both α-C-H and β-C-H bonds adjacent to the carbonyl groups are indispensable for the C-C bond cleavage. DFT calculations indicate the reaction is initiated with the oxidation of the α-C-H bond. Amines lower the activation energy of the C-C bond cleavage, and thus promote the reaction. New insight into the C-C bond cleavage mechanism is presented.