Catalysis of the Addition of Benzenethiol to 2-Cyclohexen-1-ones by Uranyl-Salophen Complexes: A Catalytic Metallocleft with High Substrate Specificity

Abstract

The base induced addition of benzenethiol to 2-cyclohexen-1-one and its 4, 4-, 5, 5- and 6,6-dimethyl derivatives is catalysed by a salophen-uranyl based metallocleft 2 in chloroform solution with high turnover efficiency and low product inhibition. Analysis of rate data coupled with equilibrium measurements for complexation of the catalyst with the enone reactants and addition products shows that the catalytic mechanism involves the three main steps typical of single-substrate enzymatic processes, namely substrate binding and recognition, transformation of the bound substrate, and release of the reaction product. Unlike the reference salophen-uranyl 1, catalyst 2 is endowed with a structured binding site responsible for a high degree of substrate specificity among the investigated enones, due to recognition of their shape and size.