The acid hydrolysis mechanism of acetals catalyzed by a supramolecular assembly in basic solution.
A self-assembled supramolecular host catalyzes the hydrolysis of acetals in basic aqueous solution. The mechanism of hydrolysis is consistent with the Michaelis-Menten kinetic model. Further investigation of the rate-limiting step of the reaction revealed a negative entropy of activation (DeltaS(double dagger) = -9 cal mol(-1) K(-1)) and an inverse solvent isotope effect (k(H(2)O)/k(D(2)O) = 0.62). These data suggest that the mechanism of hydrolysis that takes place inside the assembly proceeds through an A-2 mechanism, in contrast to the A-1 mechanism operating in the uncatalyzed reaction. Comparison of the rates of acetal hydrolysis in the assembly with the rate of the reaction of unencapsulated substrates reveals rate accelerations of up to 980 over the background reaction for the substrate 1,1-diethoxyethane.
Pluth
Michael D
MD
Department of Chemistry, University of California, Berkeley, and Division of Chemical Sciences, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA.
Bergman
Robert G
RG
Raymond
Kenneth N
KN
D000080:Acetals / Q000737:chemistry*; D002384:Catalysis; D006863:Hydrogen-Ion Concentration; D006868:Hydrolysis; D007659:Ketones / Q000138:chemical synthesis / Q000737:chemistry; D007700:Kinetics; D046911:Macromolecular Substances / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D012996:Solutions; D012997:Solvents / Q000737:chemistry; D013997:Time Factors; D014867:Water / Q000737:chemistry
D000080:Acetals; D007659:Ketones; D046911:Macromolecular Substances; D012996:Solutions; D012997:Solvents; D014867:Water