This research involves two major areas of organic synthesis. The first is the synthesis of dynemicin, which is the most biologically interesting of the diynene natural products. Based on model studies of the azabicyclo?7.3.1.!diynene core structure, the synthesis of the more complex dynemicin will be carried out by a route that incorporates the remaining oxygen substituents and allows the crucial epoxide functionality to be installed. The second area of research is synthetic methodology using the chemistry of triisopropylsilyl enol ethers, which react with electrophiles and retain the triisopropoylsilyl enol ether group.In contrast to the more commonly used trimethylsilyl group, proton loss is apparently faster than attack at silicon in the triisopropylsilyl system which opens up a whole new range of silyl enol ether chemistry. The overall transformation proceeds with remarkable stereoelectronic control. The electrophiles (Br, SePh, TsNCO, etc.) enter axially and the newly introduced substituent remains in an axial configuration. Besides the development of general methodology, the synthesis of chiral triisopropylsilyl enol ethers and their subsequent reactions will be studied. %%% With this award the Synthetic Organic Program of the Chemistry Division will support the research of Dr. Philip D. Magnus of the Department of Chemistry at the University of Texas at Austin. The research involves two major areas of organic synthetic methodology. The first is the synthesis of dynemicin which is the most biologically interesting of the diynene natural products. The second area of research is the development of the chemistry of the triisopropylsilyl enol ether functionality and the production of useful synthetic methods based upon these studies.
