Functionalization of Homodiamantane: Oxygen Insertion Reactions without Rearrangement with Dimethyldioxirane

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.