摘要
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.
基金
National Natural Science Foundation of China,Grant/Award Numbers:91940305,21933009,81874181,22271195,21871284
Natural Science Foundation of Fujian Province,Grant/Award Number:2021J01525
Major Scientific and Technological Special Project for“Significant New Drugs Creation”,Grant/Award Number:2019ZX09301158
The Emerging Frontier Program of Hospital Development Centre,Grant/Award Number:SHDC12018107
Shanghai Science and Technology Development Fund from Central Leading Local Government,Grant/Award Number:YDZX20223100001004
Shanghai Municipal Health Commission/Shanghai Municipal Administration of Traditional Chinese Medicine,Grant/Award Number:ZY(2021-2023)−0501。