Thu, Jan. 15, 2015, 3:15pm - 5:30pm
Frick Chemistry Laboratory, Taylor Auditorium
Host: Erik Sorensen
3:15 p.m. – Public research seminar, Taylor Auditorium
4:30 p.m. – Research proposal, A81
From Target-Directed Synthesis to Reactivity-Driven Methodology: Strategies to Prepare Complex Molecules
I. A general synthetic strategy for the transtaganolide and basiliolide natural products will be presented. Our approach features an Ireland–Claisen/Diels–Alder cascade reaction that rapidly provides the stereochemically complex core common to all members of the natural product family. The unprecedented oxepinone C-Ring is constructed via palladium-catalyzed annulation of a methoxyacetylide derivative. Finally, enantioselectivity is achieved via a highly asymmetric (–)-sparteine-mediated silylation reaction. The biosynthetic implications of our synthetic efforts will be discussed.
II. The utilization of aryldiazonium cations in chiral anion phase-transfer (CAPT) reactions enables the development of several enantioselective methodologies. Addition reactions of enolate and indole nucleophiles with aryldiazonium/chiral phosphate ion pairs results in enantioselective C–N bond formation. Furthermore, these ion pairs are utilized in Palladium-Heck chemistries to achieve highly enantioselective arylation. The utility of these methods is demonstrated through the preparation of enantioenriched complex molecules including macrocycles, pyrroloindolines, and conformationally –constrained tyrosine analogues.