The Cation-π Interaction in Small-Molecule Catalysis

Angew Chem Int Ed Engl. 2016 Oct 4;55(41):12596-624. doi: 10.1002/anie.201600547. Epub 2016 Jun 22.


Catalysis by small molecules (≤1000 Da, 10(-9) m) that are capable of binding and activating substrates through attractive, noncovalent interactions has emerged as an important approach in organic and organometallic chemistry. While the canonical noncovalent interactions, including hydrogen bonding, ion pairing, and π stacking, have become mainstays of catalyst design, the cation-π interaction has been comparatively underutilized in this context since its discovery in the 1980s. However, like a hydrogen bond, the cation-π interaction exhibits a typical binding affinity of several kcal mol(-1) with substantial directionality. These properties render it attractive as a design element for the development of small-molecule catalysts, and in recent years, the catalysis community has begun to take advantage of these features, drawing inspiration from pioneering research in molecular recognition and structural biology. This Review surveys the burgeoning application of the cation-π interaction in catalysis.

Keywords: cation-π interaction; homogeneous catalysis; noncovalent interactions; reaction mechanisms; stereoselective catalysis.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, U.S. Gov't, Non-P.H.S.
  • Review

MeSH terms

  • Aminopyridines / chemistry
  • Catalysis
  • Cations / chemistry
  • Cycloaddition Reaction
  • Guanidine / chemistry
  • Hydrogen Bonding
  • Lewis Acids / chemistry
  • Quantum Theory*
  • Small Molecule Libraries / chemistry*
  • Thiazoles / chemistry


  • Aminopyridines
  • Cations
  • Lewis Acids
  • Small Molecule Libraries
  • Thiazoles
  • Guanidine