Organic & Biomolecular Chemistry
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Journal Name
COMMUNICATION
DOI: 10.1039/C6OB00132G
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Scheme 4. Proposed mechanism for the OCF3-migration process.
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delineate the mechanism of the two-step synthesis of ortho-
OCF3 (hetero)arylamine derivatives. The radical trapping
experiments with TEMPO and BHT indicate that O-
trifluoromethylated hydroxylamine derivatives are formed via
radical recombination reaction between N-hydroxyl radical and
trifluoromethyl radical (·CF3). The highly negative slope (ρ =
−11.86) of the Hammett plot provides evidence for the
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Computational studies further support the reaction pathway of
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recombination of a short-lived ion pair. It is hoped that the
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Acknowledgements
This paper is dedicated to Prof. Stephen L. Buchwald on the
occasion of his 60th birthday. K.N.L., Z.L., and M.-Y.N.
acknowledge generous start-up funds from Stony Brook
University in support of this work. K.N.L. is grateful for the
fellowship from the NIH Chemical-Biology training grant
(T32GM092714). C.A.M.-R. and P.L. acknowledge generous start-
up funds from University of Pittsburgh in support of this work.
We thank TOSOH F-Tech, Inc. for their gift of TMSCF3 for the
preparation of Togni reagents. Calculations were performed at
the Center for Simulation and Modeling at the University of
Pittsburgh and the Extreme Science and Engineering Discovery
Environment (XSEDE) supported by the NSF (ACI-1053575).
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