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Metal-catalyzed alcoholysis reactions of carboxylate and organophosphorus esters

2007; Elsevier BV; Linguagem: Inglês

10.1016/s0065-3160(07)42006-8

2162-5921

R. S. Brown, Alexei A. Neverov,

Biochemical and Molecular Research

Publisher Summary This chapter elaborates the metal ion-catalyzed hydrolytic reactions of esters, amides, and organophosphorus esters. Apart from being fundamentally interesting and industrially important, phosphoryl and acyl transfer reactions are the key biological processes. Virtually, all the transition metal and lanthanide ions that have been investigated have some catalytic activity in promoting the transesterification of carboxylate esters and neutral phosphate esters. The early studies of metal-catalyzed acyl transfer reactions were predicated on the idea that a reduced polarity/dielectric constant medium would allow one to better realize the catalytic potential of the metal ion by reducing the tightness of the solvation shell around the metal ion and its constituents, as well as allow a stronger interaction energy with substrate. Despite a great deal of effort that has led to an increased understanding of how enzymatic catalysis might occur, it is generally held that none of the several models so far described approaches the enormous catalytic efficiency of natural enzymes. The ideas being discussed in this chapter will spur further work using the multiple effects of structure and medium to bring us closer to understanding the ways, in which nature performs such transformations.