Selective biomimetic epoxidations

PETR 8

Ronald Breslow, Department of Chemistry, Columbia University, 3000 Broadway, New York, NY 10027
Selectivity in biochemical reactions is achieved by the use of geometric control between the enzyme and the substrate. Such selectivity can override the intrinsic reactivities within the substrate, or between substrates. For example, oxidative enzymes can hydroxylate saturated unactivated carbons in substrates that contain double bonds or secondary alcohols, groups that are much more reactive on a simply random basis but that are not attacked by the enzyme because they are not within reach of the oxidizing species in the enzyme/substrate complex. We have developed a field we refer to as “biomimetic chemistry” to imitate this geometric control within enzyme mimics. Our first examples involved selective epoxidations, although we later extended the work to achieve the selective hydroxylations of saturated carbons.