title: Cycloaddition reactions of unactivated olefins catalyzed by an organorhenium electron-transfer mediator.
abstract: An electrochemical process is described for the rapid and efficient conversion of unsubstituted cyclic olefins into cycloaddition products. When a potential of 1.25 V vs ferrocene was applied to a solution of cis-cyclooctene (COE) in dichloromethane/[NBu(4)][B(C(6)F(5))(4)] containing a catalytic amount (4 mol %) of ReCp(CO)(3), 1, the olefin was converted to a diastereomeric mixture of the C(8)-dimer tricyclohexadecane, with the major isomer having a cis-anti-cis geometry. Smaller cyclic olefins (C(5) to C(7)) also formed cycloaddition products. The cyclization reactions require the electrogeneration of 1(+) as an electron-transfer mediator which triggers the one-electron oxidation of the olefin in spite of the fact that the potentials of the latter lie at considerably higher values. The very low coulomb count required (ca. 0.1 F per olefin) for the conversion of olefin to product is consistent with a radical-chain mechanism. The electrochemical conversion of COE to cyclized products is complete in a few minutes, in contrast to the week-long photochemical processes previously needed for preparation of the same cycloaddition products.
authors.affiliation: Department of Chemistry, University of Vermont, Burlington, Vermont 05405, USA.
authors.forename: Daesung
authors.initials: D
authors.lastname: Chong
authors.forename: Michael
authors.initials: M
authors.lastname: Stewart
authors.forename: William E
authors.initials: WE
authors.lastname: Geiger