The functionalization of carbon-oxygen bonds to form alkenes and allenes

Abstract

This dissertation focuses on investigations of activating carbon-oxygen bonds to form new carbon-carbon bonds. Chapter 1 describes one of the first examples of a carbon-carbon cross-coupling via activation of strong carbon-oxygen bond with a nonorganometallic coupling partner. It enables the transformation of phenol-based substrates into styrenyl products without generation of a halogenated waste byproduct or the use of expensive triflate groups. Chapter 2 describes the development of a magnesium mediated alkyne addition into an oxocarbenium ion to form new carbon-carbon bonds. This method represents one of the few methods for single alkenylation into an acetal substrate, and the selective formation of the E -isomer is complimentary to the metal catalyzed alkenylation of acid chlorides. It enables the construction of highly complex molecules in a single step. Chapter 3 focuses on the progress towards stereospecifically forming trisubstituted allenes from enantio enriched propargylic esters. Preliminary results, and optimization are discussed, as well as the effect of leaving group on yield and stereospecificity.