Pyridine-Boryl Radical-Enabled Reductive Radical Brook Rearrangement

Herein, we report a reductive radical Brook rearrangement enabled by a pyridine-boryl radical system, utilizing readily available N-alkoxyphthalimides as precursors. This protocol proceeds via a radical cascade of formal single-electron reduction, N–O bond fragmentation, and 1,2-silyl migration. This cascade affords nucleophilic α-silyloxy carbon radicals, which are efficiently intercepted by electron-deficient alkenes to deliver functionalized silyl ethers. The method features stable precursors, operational simplicity, and mild, thermal, metal-free, and oxidant-free conditions.