title: Functionalization of homodiamantane: oxygen insertion reactions without rearrangement with dimethyldioxirane.
abstract: Homodiamantane bromination and nitroxylation are accompanied by contraction of the seven-membered ring to give the corresponding substituted 1-diamantylmethyl derivatives. In contrast, CH-bond hydroxylations with dimethyldioxirane retain the cage and give both apically and medially substituted homodiamantanes. The product ratios are in accord with the barriers for the oxygen insertion computed with density functional theory methods only if solvation is included through a polarizable continuum model. B3LYP-D3 and M06-2X computations with a 6-31G(d,p) basis set on the oligomeric van der Waals complexes predict the potential of homodiamantane derivatives for surface modifications with conformationally slightly flexible diamondoid homologues.
authors.affiliation: Department of Organic Chemistry, Kiev Polytechnic Institute , pr. Pobedy 37, 03056 Kiev, Ukraine.
authors.forename: Andrey A
authors.initials: AA
authors.lastname: Fokin
authors.forename: Tatyana S
authors.initials: TS
authors.lastname: Zhuk
authors.forename: Alexander E
authors.initials: AE
authors.lastname: Pashenko
authors.forename: Valeriy V
authors.initials: VV
authors.lastname: Osipov
authors.forename: Pavel A
authors.initials: PA
authors.lastname: Gunchenko
authors.forename: Michael
authors.initials: M
authors.lastname: Serafin
authors.forename: Peter R
authors.initials: PR
authors.lastname: Schreiner