From simple to supramolecular cytochrome P450 mimics

Cytochrome P450 is one of Nature's oxidative workhorses and is utilized in a wide variety of roles, one of the most important being the detoxification of foreign bodies within the liver. As a result of its fundamental importance it has been extensively investigated, modeled and mimicked over the past 30 years, and more recently modified and mutated. During this period the complexity, beauty and activity of the biomimetic model systems developed in the laboratory have grown considerably. The synthetic analogues of the cytochrome P450 system have evolved dramatically fromsimple sterically hindered porphyrin models through to more complex model systems combining cavities such as cyclodextrins and utilizing the interactions between host and guest to generate substrate selectivity and stereoselectivity in product formation. More recently, researchers have tried to combine knowledge obtained from the developing field of supramolecular chemistry and from biochemistry to construct self-assembling systems that contain all the components of the natural system and even utilize molecular oxygen as the oxidant. These systems are successful in that they can achieve turnover numbers comparable to those observed for the natural system. The history of these developments and the current 'state-of-the-art' in construction of mimics of the natural enzyme will be presented.