CARBOXYLATIONS AND DECARBOXYLATIONS

A brief survey of decarboxylation reactions and carboxylation reactions that are known or presumed in biological systems will be presented. While a considerable number of amino acid decarboxylations are known, their mechanisms will not be included in the present discussion but will be reserved for a later paper in the symposium. The remaining decarboxylation reactions may be subdivided into oxidative and nonoxidative decarboxylations. In most cases, these reactions are practically irreversible except when coupled with suitable energy-yielding systems. The carboxylation reactions which are useful in the formation of carbon-carbon bonds in biological systems seem to fall into two or three groups: those which exhibit an apparent ATP requirement, and those which exhibit a reduced pyridine nucleotide requirement, and those which exhibit no apparent ATP requirement. Of the first group at least four cases, and possibly six or seven, are known, and one interpretation of them involves the preliminary formation of 'active' carbon dioxide, generally in the form of a carbonic acid-phosphoric acid anhydride. Those exhibiting no apparent ATP requirement seem to be susceptible to classifications as enol carboxylations in which the energy level of the substrate compound is high, rather than that of the carbon dioxide. There appear to be at least three examples of this latter type known, amongs them being the carboxy-dismutase reaction of ribulose diphosphate with carbon dioxide