Li Jia, Ge Shaozhong
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Singapore, Singapore.
Angew Chem Int Ed Engl. 2022 Nov 21;61(47):e202213057. doi: 10.1002/anie.202213057. Epub 2022 Oct 19.
Copper-catalyzed regioselective quadruple borylation of terminal alkynes has been developed employing a copper catalyst generated from CuI and dcpe (1,2-bis(dicyclohexylphosphino)ethane). A wide range of terminal alkynes undergo this multi-borylation reaction to afford the corresponding 1,1,2,2-tetraborylalkanes in high yields. Mechanistic studies reveal that this quadruple borylation reaction proceeds through copper-catalyzed sequential double 1,2-diborylation of alkynes and 1,2-diborylalkene intermediates. This protocol represents the most straightforward and atom-economic approach to prepare sp -tetra-organometallic reagents from readily accessible alkynes with commercially available copper catalysts.
利用由碘化亚铜和1,2-双（二环己基膦基）乙烷（dcpe）生成的铜催化剂，实现了末端炔烃的铜催化区域选择性四重硼化反应。多种末端炔烃都能发生这种多硼化反应，以高产率得到相应的1,1,2,2-四硼基烷烃。机理研究表明，这种四重硼化反应是通过铜催化的炔烃和1,2-二硼基烯烃中间体的连续双1,2-硼化反应进行的。该方法是使用市售铜催化剂从易于获得的炔烃制备sp -四有机金属试剂的最直接且原子经济的方法。
