Atroposelective Construction of Axially Chiral Tetraarylethenes Via NHC‐Catalyzed Desymmetrization

We report the first NHC-catalyzed atroposelective synthesis of axially chiral tetraarylethenes (TAEs) via oxidative desymmetrization of prochiral TAE dialdehydes. This catalytic strategy operates under mild conditions and accommodates a broad range of phenolic and nitrogen nucleophiles, delivering diverse axially chiral TAEs in good yields and up to 99% ee. The method features excellent functional-group tolerance, enables late-stage modification of complex natural products and pharmaceuticals, and is readily scalable. Furthermore, the resulting axially chiral TAEs display distinct photophysical behavior, pronounced aggregation-induced emission (AIE), and strong circularly polarized luminescence (CPL). This work establishes a general and efficient platform for constructing functional chiral TAEs with promising optoelectronic potential.