Generation and study of enols and other reactive species

A general description of methods recently developed in our laboratory for generating and studying enols and other reactive species is presented, together with an overview of the kinds of substances that have been made and the kind of information that has been obtained. This is then followed by a more detailed discussion of two systems of some biological importance, the enol of pyruvic acid and the enol of mandelic acid. Our results show that the masked enol function in phosphoenolpyruvate conmbutes half of the free energy liberated in the hydrolysis of this high-energy compound, and that racemization of mandelate ion by mandelate racemase cannot occur by enzymatically promoted enolization followed by release of enol or enolate and reketonization off the enzyme.