This thesis begins with an introduction to Vitamin E and the Jocic reaction. Chapter 1 provides a review of the biological activity of vitamin E and related compounds and the synthesis, both racemic and asymmetric, of vitamin E compounds. Also discussed in this chapter is the Jocic reaction and the synthesis of trichloromethyl alcohol compounds. Chapter 2 describes the asymmetric total syntheses of both α- and β-tocopherol, where an intramolecular Jocic reaction was used to provide a high enantiomeric excess. Difficulties encountered during the synthesis, and how these were overcome, are detailed. Chapter 3 describes the novel use of hydride as a nucleophile in the Jocic reaction with tertiary polychloromethyl alcohols. This one-carbon homologation procedure was improved by the use of dichloro- rather than trichloromethyl alcohols. The scope of the reaction, mechanisms and stereochemical implications are discussed.