Aggregation‐enabled alkene insertion into carbon–halogen bonds

Abstract

Abstract Molecular aggregation affects the electronic interactions between molecules and has emerged as a powerful tool in material science. Aggregate effect finds wide applications in the research of new physical phenomena; however, its value for chemical reaction development has been far less explored. Herein, we report the development of aggregation‐enabled alkene insertion into carbon–halogen bonds. The spontaneous cleavage of C–X (X = Cl, Br, or I) bonds generates an intimate ion pair, which can be quickly captured by alkenes in an aggregated state. Additional catalysts or promoters are not necessary under such circumstances, and solvent quenching experiments indicate that the aggregated state is critical for achieving such sequences. The ionic insertion mode is supported by mechanistic studies, density functional theory calculations, and symmetry‐adapted perturbation theory analysis. Results also show that the non‐aggregated state may quench the transition state and terminate the insertion process.

Keywords

• aggregated state chemistry
• atom‐ and step‐economy
• difunctionalization of alkenes
• ionic insertion
• solvent‐free and catalyst‐free