Chiral Perovskite Nanocrystals for Asymmetric Reactions: A Highly Enantioselective Strategy for Photocatalytic Synthesis of N–C Axially Chiral Heterocycles
Year: 2023
Type: article
Abstract: 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.
DOI: 10.1021/jacs.3c04593
Institution: San Diego State University
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: green
OpenAlex ID: W4385297545