title: Kinetics and regioselectivity in the Diels-Alder reaction of fulleroids vs. methanofullerene and C60.
abstract: Fulleroids, obtained from the 1,3-dipolar cycloaddition of fullerene with a diazoalkane, have a [5,6]-open methylene bridge and two highly twisted bridgehead double bonds. The [H,H]- and [H,CN]-substituted fulleroids were found to display significantly enhanced and regioselective Diels-Alder addition as compared with the [6,6] closed methanofullerene and C(60) with 2,3-dimethyl-1,3-butadiene, but reduced and nonregioselective addition with cyclopentadiene. NMR analysis of the 1:1 adduct and quantum calculations indicated that the high reactivity and the regioselective addition are due to pi-orbital misalignment at the bridgehead double bond.
authors.affiliation: Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Yamada-oka, Suita, Osaka 565-0871, Japan.
authors.forename: Naohiko
authors.initials: N
authors.lastname: Ikuma
authors.forename: Yasunori
authors.initials: Y
authors.lastname: Susami
authors.forename: Takumi
authors.initials: T
authors.lastname: Oshima