Frustrated Lewis Pair Mediated 1,2-Hydrocarbation of Alkynes
Frustrated Lewis Pair Mediated 1,2-Hydrocarbation of Alkynes
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受挫的路易斯对介导的炔烃的 1,2-碳氢化
DOI：
10.1002/ange.201705100
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发表时间：
2017
影响因子：
--
通讯作者：
Fasano V
中科院分区：
文献类型：
--
作者：
Fasano V
阻挫刘易斯对（FLP）化学使得能够用N-甲基吖啶鎓盐作为碳刘易斯酸进行炔1，2-加成的罕见实例。该1，2-缩合过程不像在炔合成硼氢化中那样通过协调机制进行，也不像在唯一其他报道的炔1，2-缩合反应中那样通过分子内1，3-氢化物迁移进行。相反，在这项研究中，炔1，2-缩合反应通过一种新的机制进行，该机制涉及炔与碳刘易斯酸基FLP脱炔以形成新的C-C键。随后，发生分子间氢化物转移，其中FLP的刘易斯酸组分充当氢化物穿梭，使得能够进行炔1，2-缩合。
Frustrated Lewis pair (FLP) chemistry enables a rare example of alkyne 1,2‐hydrocarbation with N‐methylacridinium salts as the carbon Lewis acid. This 1,2‐hydrocarbation process does not proceed through a concerted mechanism as in alkyne syn‐hydroboration, or through an intramolecular 1,3‐hydride migration as operates in the only other reported alkyne 1,2‐hydrocarbation reaction. Instead, in this study, alkyne 1,2‐hydrocarbation proceeds by a novel mechanism involving alkyne dehydrocarbation with a carbon Lewis acid based FLP to form the new C−C bond. Subsequently, intermolecular hydride transfer occurs, with the Lewis acid component of the FLP acting as a hydride shuttle that enables alkyne 1,2‐hydrocarbation.