The first detailed description of the catalytic racemization of activated benzylic and allylic azides under mild conditions is reported. A kinetic analysis of the observed racemization indicates a first-order dependence on azide, a first-order dependence on catalyst, and that the rate of racemization correlates to σ + . A variety of azides with varying substitution patterns undergo facile racemization, and catalyst selection can tune this process.
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We thank Prof. Megan Fieser (University of Southern California) for her many helpful discussions. Financial support was provided by the University of Minnesota and The American Chemical Society’s Petroleum Research Fund (PRF No. 56505-DNI1). This research was supported by the National Institute of General Medical Sciences of the National Institutes of Health under Award Number R35GM124718. We also acknowledge NIH Shared Instrumentation Grant No. S10OD011952.