Serendipitous Observation of AlI Insertion into a C−O Bond in L2PhB (L=Oxazol-2-ylidene)

Oxidative addition of the C−O bond in L2PhB: (L=oxazol‐2‐ylidene) to an AlI center induced ring expansion of an oxazol‐2‐ylidene ring, affording a unique organoboron species formally involving either an Al, N, O mixed heterocyclic carbene or anionic (amino)(boryl)carbene fragment. Ring expansion of an oxazol‐2‐ylidene in L2PhB (L=oxazol‐2‐ylidene) through cleavage of the C−O bond by AlI resulted in the formation of a unique organoboron species formally involving either an Al, N, O mixed heterocyclic carbene or an anionic (amino)(boryl)carbene fragment.