Synthesis and Applications of Bicyclo[1.1.0]butyl and Azabicyclo[1.1.0]butyl Organometallics

The use of metalated (aza)bicyclo[1.1.0]butanes in synthesis is currently experiencing a renaissance, as evidenced by the numerous reports in the last 5 years that have relied on such intermediates to undergo unique transformations or generate novel fragments. Since their discovery, these species have been demonstrated to participate in a wide range of reactions with carbon and heteroatom electrophiles, as well as metal complexes, to facilitate the rapid diversification of (aza)bicyclo[1.1.0]butane-containing compounds. Key to this is the relative acidity of the bridgehead C‒H bonds which promotes facile deprotonation and subsequent functionalization of an unsubstituted position on the carbon framework via the intermediacy of a metalated (aza)bicyclo[1.1.0]butane. Additionally, the late-stage incorporation of deuterium atoms in strained fragments has led to the elucidation of numerous reaction mechanisms that involve strained bicycles. The continued investigation into the inimitable reactivity of metalated bicycles will cement their importance within the field of organometallic chemistry.