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