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Scheme 3. Catalytic intermediates C and D; L ¼ Me3TACN.
philic activation of hydrogen peroxide. In order to
ascertain which mechanism is operative, further kinetic
studies are necessitated.
In conclusion, we have demonstrated the facile oxygen-
ation of organic sulfides under mild conditions. Both
catalysts A and B convert organic sulfides to their
respective sulfoxides, and then to their sulfones at com-
parable efficiencies. However, catalytic oxygenation of
CEPS, the mustard gas simulant, resulted in significant
production of the corresponding vinyl sulfone, an anal-
ogous end product generated for mustard gas from the
current decontamination protocol by using household
bleach.2 This result suggests that our catalytic conditions
may be used to decontaminate mustard gas. Contrary to
the catalytic epoxidation reactions, Mn/Me3TACN in
situ mixture did not catalyze sulfide oxygenation, illus-
trating both the significance of using well-defined Mn-
compounds and subtle mechanistic differences between
epoxidation and sulfide oxygenation.
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Acknowledgements
Financial support by the US Army Research Office
(DAAD 190110708) is gratefully acknowledged.
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References and notes
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