Carbon‐Carbon Bond Cleavage by P450 Systems

Abstract

The cytochromes P450 have long been recognized as powerful antioxidants capable of catalysing a wide variety of substrate transformations. These features are perhaps nowhere more evident than in their catalysis of C-C bong cleavage reactions. Some of these reactions are relatively simple, occuring in one mechanistic step with loss of a single, activated carbon whilst others are much more dramatic, involving multiple oxidative transformations and skeletal rearrangement and/or fragmentation of the substrate. Almost counter intuitively, these reactions are usually associated with elaborate biosynthetic pathways that build up complex secondary metabolites with significant biological activities. They are classified here according to the functional group(s) that is (are) adjacent to the site of C-C bond cleavage, even if these moieties are introduced by the P450 during the course of a multi-step oxidative transformation. Excluded from this discussion are substrates specifically designed to undergo oxidative rearrangement as mechanistic probes, such as cyclopropyl containing compounds.