title: Regioselective oxidative ring opening of cyclopropyl silyl ethers: a quantum chemical study.
abstract: In contrast to the structurally and configurationally stable alkyl- or aryl-substituted cyclopropyl radical cations, cyclopropyl silyl ethers undergo spontaneous ring opening upon oxidation whereby the endocyclic C-C(O-TMS) bond is cleaved with remarkable selectivity. DFT calculations on 1-trimethylsilyloxybicyclo[4.1.0]heptane show that this selectivity arises from the topology of the potential surface of the corresponding radical cation which is initially generated in a very steep region of the potential surface from where the steepest descent leads to cleavage of the endocyclic rather than the lateral C-C(OTMS) bond. Cleavage of the lateral bond leads to interesting conformational changes which are explored in detail.
authors.affiliation: Department of Chemistry, Bielefeld University, P.O. Box 100131, 33501 Bielefeld, Germany.
authors.forename: Heiko
authors.initials: H
authors.lastname: Rinderhagen
authors.forename: Jochen
authors.initials: J
authors.lastname: Mattay
authors.forename: Rafael
authors.initials: R
authors.lastname: Nussbaum
authors.forename: Thomas
authors.initials: T
authors.lastname: Bally