A Palladium-Catalyzed Methylenation of Olefins Using Halomethylboronate Reagents

Methylenation of electron-rich olefins is a highly challenging reaction, for which we have developed a new methodology exploiting Pd-catalysis and halomethylboronate reagents, the latter replacing diazomethane and zinc carbenoids as methylene donors. Optimization of the reaction for norbornene and extension to several other olefins are reported, with reasonable-to-excellent yields of cyclopropanes in combination with beta-H elimination products. Several mechanisms are plausible for this methylenation reaction.