An experimental and computational approach to defining structure/reactivity relationships for intramolecular addition reactions to bicyclic epoxonium ions.
In this manuscript we report that oxidative cleavage reactions can be used to form oxocarbenium ions that react with pendent epoxides to form bicyclic epoxonium ions as an entry to the formation of cyclic oligoether compounds. Bicyclic epoxonium ion structure was shown to have a dramatic impact on the ratio of exo- to endo-cyclization reactions, with bicyclo[4.1.0] intermediates showing a strong preference for endo-closures and bicyclo[3.1.0] intermediates showing a preference for exo-closures. Computational studies on the structures and energetics of the transition states using the B3LYP/6-31G(d) method provide substantial insight into the origins of this selectivity.
Wan
Shuangyi
S
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, USA.
Gunaydin
Hakan
H
Houk
K N
KN
Floreancig
Paul E
PE
D003198:Computer Simulation; D004852:Epoxy Compounds / Q000138:chemical synthesis*; D008958:Models, Molecular; D015394:Molecular Structure
D004852:Epoxy Compounds