Metal-Organic Framework with Dual Active Sites in Engineered Mesopores for Bioinspired Synergistic Catalysis

J Am Chem Soc. 2020 May 13;142(19):8602-8607. doi: 10.1021/jacs.0c02966. Epub 2020 Apr 29.

Abstract

Here we report the design of an enzyme-inspired metal-organic framework (MOF), 1-OTf-Ir, by installing strong Lewis acid and photoredox sites in engineered mesopores. Al-MOF (1), with mixed 2,2'-bipyridyl-5,5-dicarboxylate (dcbpy) and 1,4-benzenediacrylate (pdac) ligands, was oxidized with ozone and then triflated to generate strongly Lewis acidic Al-OTf sites in the mesopores, followed by the installation of [Ir(ppy)2(dcbpy)]+ (ppy = 2-phenylpyridine) sites to afford 1-OTf-Ir with both Lewis acid and photoredox sites. 1-OTf-Ir effectively catalyzed reductive cross-coupling of N-hydroxyphthalimide esters or aryl bromomethyl ketones with vinyl- or alkynyl-azaarenes to afford new azaarene derivatives. 1-OTf-Ir enabled catalytic synthesis of anticholinergic drugs Pheniramine and Chlorpheniramine.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Aza Compounds / chemical synthesis*
  • Aza Compounds / chemistry
  • Binding Sites
  • Catalysis
  • Chlorpheniramine / chemical synthesis*
  • Chlorpheniramine / chemistry
  • Cholinergic Antagonists / chemical synthesis*
  • Cholinergic Antagonists / chemistry
  • Lewis Acids / chemistry
  • Ligands
  • Metal-Organic Frameworks / chemistry*
  • Molecular Structure
  • Particle Size
  • Pheniramine / chemical synthesis*
  • Pheniramine / chemistry
  • Porosity
  • Surface Properties

Substances

  • Aza Compounds
  • Cholinergic Antagonists
  • Lewis Acids
  • Ligands
  • Metal-Organic Frameworks
  • Pheniramine
  • Chlorpheniramine