Atroposelective Arene‐Forming Wittig Reaction by Phosphorus PIII/PV=O Redox Catalysis

The Wittig reaction is renowned as exceptionally versatile method for converting a diversity of aldehydes and ketones into alkenes. Recently, strategies for chiral phosphine catalysis under PIII/PV=O redox cycling emerged to render this venerable transformation stereoselective. Herein, we describe that phosphine redox catalysis enables the enantioselective synthesis of pertinent biaryl atropisomers by means of a stereocontrolled arene-forming Wittig reaction. Key to the process is the release of an endogenous base from readily accessible tert-butyloxycarbonylated Morita-Baylis-Hillman adducts triggered by catalyst intramolecularization, permitting mild phosphine redox catalysis for atroposelective Wittig reactions. By this strategy, a broad diversity of biaryl atropisomers is obtained with up to 94:6 enantioselectivity.