Rare-Earth Catalyzed C-H Bond Alumination of Terminal Alkynes

被引:4
|
作者
Kanbur, Uddhav [1 ]
Sadow, Aaron D. [1 ]
机构
[1] Iowa State Univ, Dept Chem, 1605 Gilman Hall,2415 Osborn Dr, Ames, IA 50011 USA
基金
美国国家科学基金会;
关键词
aluminates; catalysis; C-H bond activation; rare earths; saturation kinetics; MONOMER-DIMER EQUILIBRIA; LIQUID ALUMINUM ALKYLS; SANDWICH BIS(TETRAMETHYLALUMINATE) COMPLEXES; POLYMERIZATION CATALYSTS; STRUCTURAL CHEMISTRY; METHYL COMPLEXES; CARBOALUMINATION; METALS; FUNCTIONALIZATION; ACTIVATION;
D O I
10.1002/chem.202000325
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Organoaluminum reagents' application in catalytic C-H bond functionalization is limited by competitive side reactions, such as carboalumination and hydroalumination. Herein, rare-earth tetramethylaluminate complexes are shown to catalyze the exclusive C-H bond metalation of terminal alkynes with the commodity reagents trimethyl-, triethyl-, and triisobutylaluminum. Kinetic experiments probing alkyl-group exchange between rare-earth aluminates and trialkylaluminum, C-H bond metalation of alkynes, and catalytic conversions reveal distinct pathways of catalytic aluminations with triethylaluminum versus trimethylaluminum. Most significantly, kinetic data point to reversible formation of a unique [Ln](AlR4)(2).AlR3 adduct, followed by turnover-limiting alkyne metalation. That is, C-H bond activation occurs from a more associated organometallic species, rather than the expected coordinatively unsaturated species. These mechanistic conclusions allude to a new general strategy for catalytic C-H bond alumination that make use of highly electrophilic metal catalysts.
引用
收藏
页码:5479 / 5493
页数:15
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