Cyclopropane-Fused N-Heterocycles via Aza-Heck-Triggered C(sp(3))–H Functionalization Cascades

[Image: see text] Unique examples of aza-Heck-based C(sp(3))–H functionalization cascades are described. Under Pd(0)-catalyzed conditions, the aza-Heck-type cyclization of N-(pentafluorobenzoyloxy)carbamates generates alkyl–Pd(II) intermediates that effect C(sp(3))–H palladation en route to cyclopropanes. Key factors that control the site selectivity of the cyclopropanation process have been elucidated such that selective access to a wide range of ring- or spiro-fused systems can be achieved.