The Organic and Macromolecular Chemistry Program is supporting this research which is aimed at studying the ability of novel three-membered ring compounds to introduce oxygen atoms into a variety of organic substrates in a highly specific fashion. These reagents are characterized by being relatively stable, easily handled, crystalline compounds which can be used to oxidize both acid- and base-sensitive compounds. The major objective of the ongoing research is to understand the origins of asymmetric induction (molecular recognition), in particular those forces that control the asymmetric oxidation of nonfunctionalized substrates (alkenes, sulfides and selenides). The ultimate goal of these investigations is the development of reagents and methodologies for the reagent-controlled asymmetric oxidation of prochiral substrates in high optical purity and with predictable stereochemistry. These goals are being met through the use of chiral nonracemic 2-sulfonyloxaziridines. These reagents, which have different active site structures, are uniquely qualified for studies of the origins of molecular recognition because they i) have well defined active sites, ii) are easily modified and iii) are stable. A second goal of this work is the development of catalytic oxidizing systems based on the high selectivity of 2-sulfonyloxaziridines. The prime objective here is to devise an optically active catalytic system, which mimics the efficiencies and stereoselectivities of enzymatic oxidations,i.e., artificial-enzyme catalysts. 2-Sulfonyloxaziridines are aprotic and neutral oxidizing reagents. This feature makes possible studies of unusually acid-sensitive molecules and studies of the hydroxylation of carbanions. In this regard, the chemistry of the alpha-alkoxy and alpha-amino epoxides is being explored. The oxidation of organometallic reagents (RM, vinyllithium compounds) as new routes to alcohols, phenols, lactones, enolate stereoisomers and optically active alpha-hydroxy carbonyl compounds is being pursued.
