jo4026594_si_001.pdf (1.1 MB)
Functionalization of Homodiamantane: Oxygen Insertion Reactions without Rearrangement with Dimethyldioxirane
journal contribution
posted on 2014-02-21, 00:00 authored by Andrey A. Fokin, Tatyana S. Zhuk, Alexander E. Pashenko, Valeriy V. Osipov, Pavel A. Gunchenko, Michael Serafin, Peter R. SchreinerHomodiamantane 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.
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oligomeric van der Waals complexescomputationdimethylmediallyoxygen insertiondiamondoid homologuesFunctionalizationOxygen Insertion Reactionsnitroxylationbarrierdensityhydroxylationb 3LYPapicallytheory methodsderivativecontrastsolvationDimethyldioxiraneHomodiamantane brominationsurface modificationsRearrangementcagecontractionproduct ratiosaccordbasisconformationallypolarizable continuum model
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