Regioselective α-Amination of Ethers Using Stable N-Chloroimides and Lithium tert-Butoxide

Herein we describe a metal-free regioselective alpha-amination of ethers mediated by N-chloroimides in ethereal solvents in the presence of lithium tert-butoxide. This reactivity of N-chloroimides leads to the synthesis of hemiaminal ethers in good to excellent yields at room temperature. This C-H functionalization is achieved without the use of a light, heat source, or external radical initiators. Initial mechanistic work indicates that the reaction proceeds through a radical pathway.