Atroposelective Synthesis of Axially Chiral Diaryl Ethers via Organocatalyzed Enantioselective Desymmetric Allyl Addition

Abstract

Catalytic asymmetric construction of C─O axially chiral diaryl ethers remains underdeveloped relative to C─C biaryl atropisomers, and examples that simultaneously create a stereogenic carbon center are scarce. Herein, we report a chiral phosphoric acid‐catalyzed enantioselective allyl addition of prochiral dialdehydes with allylboronate, which enables the efficient synthesis of a novel class of axially chiral diaryl ethers bearing both C─O axial chirality and a stereogenic benzylic carbon center. This protocol provides the desired products in good diastereoselectivities and enantioselectivities under mild conditions. The retained aldehyde group serves as a versatile handle for diverse downstream transformations, substantially enhancing the structural and functional diversity of the atropisomeric scaffolds.