Development of environmentally friendly syntheses: use of enzymes and biomimetic systems for the direct carboxylation of organic substrates.

Carboxylation reactions widely occur in nature by the direct use of carbon dioxide or hydrogen carbonate and are mediated by enzymes, which may or may not have a metal as an active center. Such direct carboxylation reactions have found only very few applications for synthetic purposes at industrial level. In this paper we review a part of the work we have done on the use of carbon dioxide and describe: (i) the use of a carboxylation enzyme for the conversion of phenol into 4-OH benzoic acid; and (ii) the potential of biomimetic mixed anhydrides for the synthesis of compounds of industrial interest. The enzymatic production of acetic acid from carbon dioxide is compared with known and new transition metal catalyzed reactions that are fully biomimetic.