title: Electrophile-induced C-C bond activation of vinylcyclopropanes for the synthesis of Z-alkylidenetetrahydrofurans.
abstract: We present a detailed study on the behavior of vinylcyclopropanes as masked donor-acceptor system toward the stereoselective synthesis of Z-alkylidenetetrahydrofurans. Results of bromenium catalyzed indirect activation of C-C bond of vinylcyclopropanes and concomitant cyclization to alkylidenetetrahydrofuran and other heterocycles have been discussed. The stereoselective formation of the Z-isomer is strongly controlled by the extent of destabilization of one of the gauche conformers of the vinylcyclopropane. The ring-opening/cyclization step was found to be stereospecific as in the case of DA cyclopropanes. The activation of the C-C bond leads to a tight-carbocation intermediate, which is evident from the complete retention of the stereochemistry. The retention of configuration has been established by a necessary control experiment that rules out the possibility of a double inversion pathway. The present results serve as direct stereochemical evidence in support of a tight ion-pair intermediate versus the controversial S(N)2 pathway. A 2D potential energy scan has been carried out at B3LYP/6-31G(d) level theory to obtain the relative energies of the conformers. The Z-selectivity observed has been explained on the basis of the relative population of the conformers and modeling the intermediate and transition state involved in the reaction at M06-2x/6-31+G(d) level. Energy profile for the cyclization step was modeled considering various possible pathways through which cyclization can happen. The methodology has been successfully demonstrated on vinylcyclobutanes as well.
authors.affiliation: Department of Organic Chemistry, Indian Institute of Science, Bangalore-560 012, Karnataka, India.
authors.forename: Venkataraman
authors.initials: V
authors.lastname: Ganesh
authors.forename: Taraknath
authors.initials: T
authors.lastname: Kundu
authors.forename: Srinivasan
authors.initials: S
authors.lastname: Chandrasekaran