Ross Widenhoefer

Mechanistic Studies of Palladium-catalyzed Diene Carbocyclizations Ross Widenhoefer

Synthetic chemists believe that with a fundamental understanding of mechanisms of transition metal-catalyzed reactions, it may be possible to design better catalysts and to more accurately predict the outcomes of transition metal-catalyzed reactions. This book describes a thorough case study. Based on the results of our mechanistic study of the cycloisomerization of functionalized 1,6-dienes a simple bidentate nitrogen ligand on the palladium atom works as well as one with electron donating or withdrawing groups. Furthermore, the rate of cycloisomerization is dependent on the homoallylic substituent and its ability to form an oxochelate complex. The rate and selectivity of the cyclization/hydrosilylation of functionalized 1,6-dienes is intimately tied to the stereochemistry and size of the terminal olefinic position. For chemists interested in transition metal-catalyzed carbon-carbon bond formation or the experimental methodologies involved in mechanistic studies this book provides an introduction.