This report describes the stereoselective synthesis of 3-azido-tetralins, -chromanes, and -tetrahydroquinolines via a tandem allylic azide rearrangement/Friedel-Crafts alkylation. Exposure of allylic azides with a pendant trichloroacetimidate to catalytic quantities of AgSbF proved optimal for this transformation. This cascade successfully differentiates the equilibrating azide isomers, providing products in excellent yield and selectivity (>25 examples, up to 94% yield and >25:1 dr). In many cases, the reactive isomer is only a trace fraction of the equilibrium mixture, keenly illustrating the dynamic nature of these systems. We demonstrate the utility of this process via a synthesis of hasubanan.

A highly regioselective Wacker oxidation has been developed for the oxidation of cinnamyl azides. The catalytic oxidation tolerates the azide functionality, and more than 15 β-azido ketones were isolated (25-92% yield). High regioselectivity for the aryl ketone is observed in all cases. A robustness screen was conducted to determine functional group tolerance. The products of the oxidaiton can be readily diversified.