A Boratafulvene.

Structurally authenticated free B-alkyl boroles are presented and electronic implications of alkyl substitution were assessed. Deprotonation of a boron-bound exocyclic methyl group in a B-methyl borole yields the first 5-boratafulvene anion-an isomer to boratabenzene. Boratafulvene was structurally characterized and its electronic structure probed by DFT calculations. The pK value of the exocyclic B-CH in a set of boroles was computationally approximated and confirmed a pronounced acidic character caused by the boron atom embedded in an anti-aromatic moiety. The non-aromatic boratafulvene reacts as a C-centered nucleophile with the mild electrophile Me SnCl to give a stannylmethyl borole, regenerating the anti-aromaticity. As nucleophilic synthons for boroles, boratafulvenes thus open an entirely new avenue for synthetic strategies toward this highly reactive class of heterocycles. Boratafulvene reacts as a methylene transfer reagent in a bora-Wittig-type reaction generating a borole oxide.