10.1002/chem.201804957
Chemistry - A European Journal
COMMUNICATION
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In conclusion, we synthesized 14 pseudocyclic NHIs and
elucidated the solid state structure of 7 diverse derivatives. We
demonstrated that the stabilizing ortho-N-heterocycle is capable
to modulate the central I-O1 bond length in (hydroxy)aryl-λ3-
iodanes in a so far unseen variety and significantly impacts the
reactivity of the iodane in the oxidation of sulfides as a model
reaction. We finally demonstrated that these NHIs can be easily
converted into other classes of hypervalent iodine compounds, in
particular diaryliodonium salts and cyclic arylbenziodazoles. This
is the first systematic investigation of pseudocyclic NHIs and we
are confident that this report will inspire other researches to
develop and fine tune hypervalent iodine compounds as group
transfer reagents based on this concept using N-heterocycles as
stabilizing ortho-substituents. Further investigations towards
applications and derivatisations of NHIs are under on-going
investigation in our laboratories.
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Acknowledgements
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We
gratefully
acknowledge
the
DFG
(Deutsche
[30] During submission of this manuscript,
a
detailed analysis of
and
benzimidazole-stabilized [hydroxy-(tosyloxy)iodo]arenes
Forschungsgemeinschaft (Grant NA955/3-1)) and the Fonds der
Chemischen Industrie (PhD-stipend to AB) for financial support.
diaryliodoniumsalts was reported: Y. A. Vlasenko, P. S. Postnikov, M. E.
Trusova, A. Shafir, V. V. Zhdankin, A. Yoshimura, M. S. Yusubov, J. Org.
Chem. 2018; DOI: 10.1021/acs.joc.8b01995.
Keywords: hypervalent iodine • heterocycles • oxidation •
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molecular diversity • substituent effects
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