Novel methods in electron transfer chemistry

Chapter 1. Electrochemical formation of glycals. An updated electrochemical approach to the formation of glycals is presented. This important intermediates are typically formed by the reduction of glycosyl halides with a variety of reductants. Electrochemistry offers a simplified and environmentally friendly approach to the synthesis of these materials.; Chapter 2. Titanocene(III)-mediated formation of C-glycosides . A one-pot preparation of C-glycosides from glycals is presented. Epoxidation of the glycal followed by reduction with titanocene(III) chloride generates a glycosyl radical which can be trapped with a variety of electron-poor olefins and other trapping agents. The method is stereoselective in most cases to provide α-C-glycosides.; Chapter 3. Titanocene(III)-mediated Reformatsky reaction. Titanocene(III) chloride is employed as alternative reductant to affect the Reformatsky addition of α-halo esters to a variety of aldehydes. The addition is stereospecific to predominantly afford the anti aldol adduct.; Chapter 4. Enzymatic bromo-cyclizations with vanadium bromoperozidase . The use of vanadium bromoperoxidase as a brominating agent for simple terpenes is explored. The brominated products received from our model reactions are in many cases reminiscent of known natural products found in sea algae.