Enantioselective Synthesis of Five to Eight‐Membered P‐Stereogenic Benzo‐Fused Heterocycles via Copper‐Catalyzed Dynamic Kinetic Resolution

Abstract P‐stereogenic benzo‐fused heterocycles is a privileged skeleton due to their outstanding catalytic properties and bioactivities. However, their enantioselective synthesis is still underdeveloped. Here we demonstrate the use of easily accessible racemic H−P(O) compounds as starting materials and commercial chiral N 1 , N 2 ‐dimethyl‐1,2‐diphenylethane‐1,2‐diamine ligand in combination with Cu(I) catalysts to enable an attractive dynamic kinetic C( sp 2)−P cross‐coupling reaction. This protocol not only exhibits a broad substrate scope but also provides general access to a diverse range of useful P‐stereogenic five‐, six‐, seven‐ and eight‐membered benzo‐fused O, P‐ containing heterocycles with good to high yields and enantioselectivities.