Dynamic combinatorial libraries kinetic

Polyakov VA, Nelen MI, Nazarpack-Kandlousy N, Ryabov AD, Eliseev AV. Imine exchange in 0-aryl and 0-alkyl oximes as a base reaction for aqueous dynamic combinatorial libraries. A kinetic and thermodynamic study. J Phys Org Chem 1999 12 357-363. 

A templated process can be driven thermodynamically or kinetically [23]. In the former case, the template binds more strongly to one of the products present in an equUibriiun (i.e., a mixture imder thermodynamic control) shifting the reaction towards the formation of this specific product which is then obtained in higher yields. As will be discussed later in this review, this is particularly important in the generation of dynamic combinatorial libraries. On the other hand, kinetic templates operate under irreversible conditions by stabilising the transition state leading to the final product. 

Dynamic combinatorial nitroaldol libraries were also used to illustrate iDCR [5,6], In this case, one of the library components was selected for its possibility to undergo an irreversible tandem cyctizafion reaction following equilibrium formation. This provided an internal kinetic selection pressure on the library, subsequently forcing the library to complete amplification of this novel reaction product. Furthermore, interesting crystalline properties were observed for one of the diastereoisomers of this isoindolinone-type product, providing a route to demonstrate consecutive resolution processes resolving coupled DCLs in a one-pot experiment. 

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