Chiral Perovskite Nanocrystals for Asymmetric Reactions: A Highly Enantioselective Strategy for Photocatalytic Synthesis of N-C Axially Chiral Heterocycles.

Catalytic approaches to generate enantiospecific chiral centers are the major premise of modern organic chemistry. Heterogeneous catalysis is responsible for the vast majority of chemical transformations, yet the direct employment of chiral solid catalysts for asymmetric synthesis is mostly overlooked. Here, we demonstrated that a heterogeneous metal-halide perovskite nanocrystal (NC) catalyst is active for asymmetric organic synthesis under visible-light activation. Chiral 1-phenylethylamine (PEA)-hybridized perovskite PEA/CsPbBr 3 NC photocatalysts exhibit an enantioselective (up to 99% enantiomer excess, ee) avenue to produce N-C axially chiral N-heterocycles, i.e., N -arylindoles from N -arylamine photo-oxidation. Mechanistic investigation indicated a discriminated prochiral binding of the N -arylamine substrates onto the chiral-NC surface with ca. -2.4 kcal/mol enantiodifferentiation. Our perovskite NC heterogeneous catalytic system not only demonstrates a promising strategy to address the long-term challenges in atroposelective pharmaceutical scaffold synthesis but also paves the road to directly employ chiral solids for asymmetric synthesis.