Reactivities of α-Oxo BMIDA Gold Carbenes Generated by Gold-Catalyzed Oxidation of BMIDA-Terminated Alkynes.
Reactivities of α-Oxo BMIDA Gold Carbenes Generated by Gold-Catalyzed Oxidation of BMIDA-Terminated Alkynes.
复制标题
金催化氧化 BMIDA 封端的炔烃生成的 α-Oxo BMIDA 金卡宾的反应性。
DOI：
10.1002/anie.202218175
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Zhang,Liming
中科院分区：
文献类型：
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作者：
Zheng,Yang;Jiang,Jingxing;Li,Yue;Wei,Yongliang;Zhang,Junqi;Hu,Jundie;Ke,Zhuofeng;Xu,Xinfang;Zhang,Liming
报道了一种直接从BMIDA封端的炔获得α-氧代BMIDA金卡宾的氧化策略。这些BMIDA金卡宾除了提供了一个很好的途径来合成硼基金属卡宾外，还可以在没有索普-英戈尔德效应的情况下，很容易地插入到甲基、亚甲基、次甲基和苄基的C−H键中。它们也会进行有效的OH插入、环丙烷化和F-C烷基化。这种化学性质提供了快速获得结构多样的α-BMIDA酮的途径，而这种途径几乎没有文献记载。结合DFT研究，BMIDA的作用被确定为是一种供电子基团，其减弱了金卡宾中心的高亲电性。
An oxidative strategy is reported to access α‐oxo BMIDA gold carbenes directly from BMIDA‐terminated alkynes. Besides offering expedient access to seldom studied boryl metal carbenes, these BMIDA gold carbene species undergo facile insertions into methyl, methylene, methine, and benzylic C−H bonds in the absence of the Thorpe–Ingold effect. They also undergo efficient OH insertion, cyclopropanation, and F−C alkylations. This chemistry provides rapid access to structurally diverse α‐BMIDA ketones, which are scarcely documented. In combination with DFT studies, the role of BMIDA is established to be an electron‐donating group that attenuates the high electrophilicity of the gold carbene center.