Carbon-carbon Bond Forming Reactions Facilitated by Kukhtin-ramirez Adducts

Open Access
Author:
Damiano, Samantha Frances
Graduate Program:
Chemistry
Degree:
Master of Science
Document Type:
Master Thesis
Date of Defense:
December 09, 2014
Committee Members:
  • Alexander Thomas Radosevich, Thesis Advisor
Keywords:
  • Oxyphosphoranes
  • Carbon-Carbon Bond Forming Reactions
Abstract:
The preparation of carbon-carbon bonds is an essential goal of organic synthesis. This thesis describes research efforts directed toward the use of Kukhtin-Ramirez type oxyphosphoranes derived from α-ketoesters as reagents to initiate carbon-carbon bond formation in three transformations. First, a non-metal mediated Barbier-type addition is described with diastereoselection under both substrate and reagent control. Second, diastereoselective epoxidation resulting from reaction of Kukhtin-Ramirez adducts with aldehydes is described and the impact of Lewis acid additives on diastereoselection is explored. Third, the potential of Kukhtin-Ramirez adducts as carbene transfer precursors in transition metal-catalyzed reactions is investigated within the context of cyclopropanation and insertion reactions. Concisely, this thesis explores the ambiphilic properties of Kukhtin-Ramirez adducts by attempting to carry out new carbon-carbon bond forming reactions.