Reductive 1,2-diboration of alkynes has been accomplished by means of sodium dispersion in the presence of trimethoxyborane as a reduction-resistant boron electrophile. Two boron moieties can be introduced onto alkynes with excellent syn selectivity to afford the corresponding (Z)-1,2-diborylalkenes. Bis(borate) species generated in situ can be involved in one-pot Suzuki-Miyaura arylation, formal arylboration of alkynes thus being executed.

Treatment of benzotrifluorides with sodium dispersion in the presence of bis(pinacolato)diboron results in diborative reduction to yield the corresponding diborylbenzylsodium species. The anionic species react not only with reactive organic halides but also with aromatic carbonyl compounds to yield the corresponding alkenylboron compounds via Peterson-type olefination. The success of the generation of the diborylbenzylsodium species lies in immediate capture of initially formed unstable difluorobenzylsodium with co-existing reduction-resistant bis (pinacolato)diboron.