Format

Send to

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

The Cation-π Interaction in Small-Molecule Catalysis.

Author information

1
Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford St, Cambridge, MA, 02138, USA.
2
Department of Chemistry, University of California, Berkeley, 535 Latimer Hall, Berkeley, CA, 94720, USA.
3
Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford St, Cambridge, MA, 02138, USA. jacobsen@chemistry.harvard.edu.

Abstract

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

PMID:
27329991
PMCID:
PMC5096794
DOI:
10.1002/anie.201600547
[Indexed for MEDLINE]
Free PMC Article

Supplemental Content

Full text links

Icon for Wiley Icon for PubMed Central
Loading ...
Support Center