Cobalt catalyzed practical hydroboration of terminal alkynes with time-dependent stereoselectivity
Jinglan Wen, Yahao Huang, Yu Zhang, Hansjörg Grützmacher, Peng Hu
Abstract
Abstract Stereodefined vinylboron compounds are important organic synthons. The synthesis of E −1-vinylboron compounds typically involves the addition of a B-H bond to terminal alkynes. The selective generation of the thermodynamically unfavorable Z -isomers remains challenging, necessitating improved methods. Here, such a proficient and cost-effective catalytic system is introduced, comprising a cobalt salt and a readily accessible air-stable CNC pincer ligand. This system enables the transformation of terminal alkynes, even in the presence of bulky substituents, with excellent Z -selectivity. High turnover numbers (>1,600) and turnover frequencies (>132,000 h −1 ) are achieved at room temperature, and the reaction can be scaled up to 30 mmol smoothly. Kinetic studies reveal a formal second-order dependence on cobalt concentration. Mechanistic investigations indicate that the alkynes exhibit a higher affinity for the catalyst than the alkene products, resulting in exceptional Z -selective performance. Furthermore, a rare time-dependent stereoselectivity is observed, allowing for quantitative conversion of Z -vinylboronate esters to the E -isomers.