Physical Sciences and Mathematics Commons^™

Electronic Structure Evaluation Of Competing Pathways In The Gold(Iii)-Catalyzed Ohloff-Rautenstrauch Cyclosimerization Converting Propargylic Acetates To Carene-Like Natural Products, Jeremy M. Hines

MSU Graduate Theses

Propargylic acetates can lead to complex transformations upon exposure to a gold catalyst. Gold catalyzed transformations also allow for simple synthesis of a number of natural products. Gold (III)-cycloisomerization of a 5-acetoxy-1,6-enyne is reported to proceed through two pathways that differ in the order of major events: cyclization followed by ester migration (“cyclization first”) or the reverse (“migration first”). Both pathways could theoretically proceed in either order. This rearrangement is called the Ohloff-Rautenstrauch rearrangement and has high regio- and stereocontrol affording a bicylo[4.1.0]heptane carbon substructure. This rearrangement allows for the synthesis of the carene class of natural products. Computational modeling …