Epoxide Synthesis via Energy-Transfer-Enabled 1,4-Nitrogen Migration

Abstract Epoxides are privileged scaffolds in synthetic chemistry, serving as key precursors for amino alcohols and pharmaceuticals. Traditional strategies to access valuable α-amino epoxides often face limitations in selectivity and require harsh conditions. Inspired by the classic di-π-methane rearrangement, we have developed a visible-light-driven alternative that triggers an unprecedented 1,4-nitrogen migration via an oxa-π,σ-methane rearrangement mechanism. This energy-transfer-catalysis process efficiently converts readily available allylic alcohols into α-amino-substituted epoxides under mild conditions. This method provides a direct and versatile route to these high-value building blocks, bypassing previous synthetic bottlenecks. We describe the discovery and mechanical insights of this new reaction paradigm in detail.