Thermal EDA-Mediated Divergent Synthesis of Acetimidates and Benzochromenes via a One-Pot Three-Component Reaction

A metal-, light-, catalyst-, and additive-free divergent synthesis of acetimidates and benzochromenes has been established from [1,1′-binaphthalene]-2,2′-diols (BINOLs) and aryldiazonium salts by using MeCN as the imine source with its cyano carbon serving as the C1 synthon. The electron donor–acceptor (EDA) complex-mediated radical pathway delivers two scaffolds controlled solely by phenolic ortho substituents: H for acetimidates and aryl groups for benzochromenes. It inhibits Ritter-type side reactions, tolerates diverse functional groups, scales well, and retains axial chirality, offering a practical route to chiral building blocks.