Photoactive chiral metal-organic frameworks for light-driven asymmetric α-alkylation of aldehydes

J Am Chem Soc. 2012 Sep 12;134(36):14991-9. doi: 10.1021/ja305367j. Epub 2012 Aug 31.


Chiral metal-organic frameworks (MOFs) with porous and tunable nature show promise as heterogeneous asymmetric catalysts. Through incorporating the stereoselective organocatalyst L- or D-pyrrolidin-2-ylimidazole (PYI) and a triphenylamine photoredox group into a single framework, we have developed two enantiomeric MOFs, Zn-PYI1 and Zn-PYI2, to prompt the asymmetric α-alkylation of aliphatic aldehydes in a heterogeneous manner. The strong reductive excited state of the triphenylamaine moiety within these MOFs initiated a photoinduced electron transfer, rendering an active intermediate for the α-alkylation. The chiral PYI moieties acted as cooperative organocatalytic active sites to drive the asymmetric catalysis with significant stereoselectivity. Control experiments using the lanthanide-based metal-organic frameworks Ho-TCA and MOF-150, assembled from 4,4',4"-nitrilotribenzoic acid, as catalysts suggested that both the photosensitizer triphenylamine moiety and the chiral organocatalyst D-/L-PYI moiety were necessary for the light-driven α-alkylation reactions. Further investigations demonstrated that the integration of both photocatalyst and asymmetric organocatalyst into a single MOF makes the enantioselection superior to that of simply mixing the corresponding MOFs with the chiral adduct. The easy availability, excellent stereoselectivity, great separability, and individual components fixed with their well-defined porous and repeating structures make the MOF a versatile platform for a new type of tandem catalyst and cooperative catalyst.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Aldehydes / chemical synthesis
  • Aldehydes / chemistry*
  • Alkylation
  • Crystallography, X-Ray
  • Light*
  • Models, Molecular
  • Molecular Structure
  • Organometallic Compounds / chemical synthesis
  • Organometallic Compounds / chemistry*
  • Photochemical Processes
  • Zinc / chemistry


  • Aldehydes
  • Organometallic Compounds
  • Zinc