The Organic and Macromolecular Chemistry Program is supporting this project which deals with the development of novel sulfur- and phosphorus-containing reagents to be used to prepare a variety of naturally occurring compounds of biological importance. These reagents are designed to carry out a wide variety of important organic reactions, many of them with an unusually high degree of stereospecificity. The enantioselective formation of carbon-carbon bond is extremely important in the synthesis of chiral organic molecules. Recently, this research group has developed a general and facile process for annulation which allows the preparation of these ring compounds in high to excellent optical purities, i.e. 1,4 gamma-addition of chiral sulfinylallyl anions to cyclic enones provided 70-97% ee, and chiral allylphosphonyl anions provided 88-98% ee. Studies of the general scope, mechanism and versatility of these stereospecific 1,4-addition reactions of chiral sulfinyl- and phosphonylallyl anions will provide better understanding of the structures of the anions and further information on their utility in organic synthesis. Enantioselective total syntheses of antitumor agents, trichothecenes, indolizidine alkaloids, and many other diterpenoids will be realized by utilizing these methods.
