title: Intramolecular carbolithiation cascades as a route to a highly strained carbocyclic framework: competition between 5-exo-trig ring closure and proton transfer.
abstract: The preparation of fairly strained carbocyclic ring systems by intramolecular 5-exo-trig ring closure has been well documented, and the absence of proton transfers that would compromise such cyclizations is a hallmark of this chemistry. In an effort to explore the limitations of this approach to more highly strained systems, the preparation of a stellane (tricyclo[3.3.0.0(3,7)]octane) framework by an intramolecular carbolithiation cascade involving three coupled 5-exo-trig cyclizations of the vinyllithium derived from 2-bromo-4-vinyl-1,6-heptadiene by lithium-bromine exchange was investigated. The cascade does not afford the stellane; rather, the cascade is terminated after two cyclizations by a proton transfer that occurs by an intermolecular process catalyzed by trace amounts of endo-5-methyl-2-methylenebicyclo[2.2.1]heptane present in reaction mixtures as a consequence of inadvertent quenching of an intermediate alkyllithium during prolonged reaction times at room temperature.
authors.affiliation: Department of Chemistry, University of Connecticut, Storrs, Connecticut 06269-3060, USA.
authors.forename: William F
authors.initials: WF
authors.lastname: Bailey
authors.forename: Justin D
authors.initials: JD
authors.lastname: Fair
keywords: carbolithiation cascade; carbometallation; intermolecular proton transfer; intramolecular carbolithiation; lithium–halogen exchange; strained hydrocarbons