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ID 31185
file
creator
Yamaguchi, Torahiko
Fuku-en, Shin-ichi
Sugawara, Shun
NDC
Chemistry
abstract
With the objective of preparing an isolable triplet carbene, we have carried out the oxidation of an allenic compound bearing two thioxanthene moieties (5). Relatively weak oxidants such as Ph3C+BF4 – gave 8, which is the conjugate acid of 5, as a result of a one-electron oxidation followed by hydrogen abstraction, whereas relatively strong oxidants such as SbCl5 furnished a dicationic ketal (9) as a consequence of oxidation and demethylation. Computations on the supposed dicationic intermediate suggest that the singlet state is more stable than the triplet state by 6.7 kcal mol–1 and that the reason for this peculiarity is because the singlet state is essentially a vinyl cation stabilized by a coordinating methoxy group.
journal title
Australian Journal of Chemistry
volume
Volume 63
issue
Issue 12
start page
1638
end page
1644
date of issued
2010-12-06
publisher
CSIRO Publishing
issn
0004-9425
ncid
publisher doi
language
eng
nii type
Journal Article
HU type
Journal Articles
DCMI type
text
format
application/pdf
text version
author
rights
Copyright (c) 2010 CSIRO
relation url
department
Graduate School of Science