The homoleptic lanthanide complex Sm[N(TMS)2]3 is an efficient rare-earth catalyst for the hydroboration of alkynes to the corresponding alkenylboron compounds. Practical applications were demonstrated in a gram-scale synthesis and further...

Lithium-promoted hydroboration of alkynes and alkenes using commercially available hexamethyldisilazane lithium as a precatalyst and HBpin as a hydride source has been developed. This method will be appealing for organic synthesis because of its remarkable substrate tolerance and good yields. Mechanistic studies revealed that the hydroboration proceeds through the in situ-formed BH3 species, which acts to drive the turnover of the hydroboration of alkynes and alkenes.