SN2 Reactions at Tertiary Carbon Centers in Epoxides

Described herein is a novel concept for S_N2 reactions at tertiary carbon centers in epoxides without activation of the leaving group. Quantum chemical calculations show why S_N2 reactions at tertiary carbon centers are proceeding in these systems. The reaction allows flexible synthesis of 1,3‐diol building blocks for natural product synthesis with excellent control of the relative and absolute configurations.