Borylative Radical Cyclizations of Benzo[3,4]cyclodec-3-ene-1,5-diynes and N-Heterocyclic Carbene-Boranes.

Borylative radical cyclization of benzo[3,4]cyclodec-3-ene-1,5-diynes to provide 5-borylated 6,7,8,9-tetrahydrobenzo[a]azulenes has been developed. The experimental results suggest that the reaction proceeds by a radical chain mechanism, in which di-tert-butyl hyponitrite (TBHN) works as a good radical initiator to form boryl radicals from N-heterocyclic carbene-boranes (NHC-boranes). The present reaction is a rare model that illustrates addition of boryl radicals to alkynes.