Development of E-and Z-Selective Base-Catalyzed Redox Isomerizations and Ene-Diene Cross Metathesis

by Sonye, John P.

?-Oxo-?,?-alkenoates are found in several natural products and are versatile synthetic intermediates. We have developed methods to selectively prepare E and Z-alkenoates from ?-hydroxy-?,?-alkynoates wherein the optimization, mechanism, and scope of the reactions are described. Biological testing of ?-oxo-?,?-alkenoates and their derivatives in zebrafish embryos also are discussed. Since the development of ruthenium alkylidene catalysts, olefin metathesis has become a useful method in synthetic organic chemistry. However, certain areas of metathesis have remained under-researched; in particular, the cross metathesis of a 1,3-diene with a terminal olefin known as ene-diene cross metathesis (EDCM). The attempt at optimization of EDCM reactions using a general model is also discussed.