Synthesis of α,β-Unsaturated Aldehydes Based on a One-Pot Phase-Switch Dehydrogenative Cross-Coupling of Primary Alcohols

An efficient <i>one-pot</i> ruthenium-catalyzed hydrogen-transfer strategy for a direct access to α,β-unsaturated aldehydes has been developed. The employment of enolates prepared in situ from alcohols avoided handling unstable aldehydes and provided a very appealing route to different cinnamaldehydes substituted in position 2. A silica-grafted amine was used as phase-switch tag leading to a selective one-pot process in favor of cross-dehydrogenative coupling products.