Chemistry and Catalysis in Functional Cavitands

Overview

Journal Chem Biol

Publisher Elsevier

Specialties Biochemistry
Biology
Chemistry

Date 2009 Mar 26

PMID 19318207

Citations 36

Authors

Richard J Hooley

Julius Rebek Jr

Affiliations

Soon will be listed here.

Abstract

Biological macromolecules use binding forces to access unfavorable chemical equilibria and stabilize reactive intermediates by temporarily isolating them from the surrounding medium. Certain synthetic receptors, functional cavitands, share these abilities and allow for the direct observation of labile intermediates by conventional spectroscopy. The cavitands feature inwardly directed functional groups that form reversible, covalent bonds with small molecules held inside. Tetrahedral intermediates of carbonyl addition reactions--hemiaminals, hemiacetals, and hemiketals--show amplified concentrations and lifetimes of minutes under ambient conditions. Labile intermediates in addition reactions of carboxylic acids to isonitriles are also stabilized by isolation in the space of the cavitands. The restricted environments channel the reactions of intermediates in cavitands along a specific path and strengthen the parallels between functional synthetic cavitands and enzymes.

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