Functionalization of Homodiamantane: Oxygen Insertion Reactions without Rearrangement with Dimethyldioxirane Andrey A. Fokin Tatyana S. Zhuk Alexander E. Pashenko Valeriy V. Osipov Pavel A. Gunchenko Michael Serafin Peter R. Schreiner 10.1021/jo4026594.s001 https://acs.figshare.com/articles/journal_contribution/Functionalization_of_Homodiamantane_Oxygen_Insertion_Reactions_without_Rearrangement_with_Dimethyldioxirane/2321170 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. 2014-02-21 00:00:00 oligomeric van der Waals complexes computation dimethyl medially oxygen insertion diamondoid homologues Functionalization Oxygen Insertion Reactions nitroxylation barrier density hydroxylation b 3LYP apically theory methods derivative contrast solvation DimethyldioxiraneHomodiamantane bromination surface modifications Rearrangement cage contraction product ratios accord basis conformationally polarizable continuum model