Development of catalysts for the addition of N-H and O-H to carbon-carbon double bonds

• Main Author: Taylor, Jason Guy
• Other Authors: Hii, Mimi
• Published: Imperial College London 2008
• Subjects: 541.39
• Online Access: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.486810

The addition of O-H and N-H bonds across carbon-carbon double bonds offers a direct way of synthesising a variety of organic molecules. These reactions have attracted considerable interest in academic research and the chemical/pharmaceutical industry in recent years due to its atom economy. Nevertheless, there remains a considerably challenge to control the regioselectivity and the stereoselectivity of this reaction. This PhD thesis describes the investigation into the discovery and development of a general method for catalytic hydroamination (HA), hydroalkoxylation and hydrooxyacylation of olefins. Air- and moisture-stable transition metal catalysts were the main focus of this study. The introductory Chapter provides an overview of recent advances in N-H addition reactions involving late transition metal catalysts. In Chapter 2, rhodium and ruthenium complexes were examined as catalysts for the addition of N-H bonds to alkenes. The combination of (RuCl2)n/dppb/AgOTf generated a catalyst effective for the addition of methyl carbamate to norbornene in a modest yield. Copper (II) trifluoromethanesulfonate was discovered to be an efficient catalyst for the addition of carboxylic acids, phenols and alcohols to norbornene. A selection of norbornyl esters and ethers were formed in good to excellent yields. In the following Chapter, the combination of copper (II) trifluoromethanesulfonate and diphosphine ligands was successfully applied to the addition of sulfonamides and carbamates to vinylarenes, 1,3-dienes and norbornene in good to excellent yields. In Chapter 4, the intramolecular hydroamination reaction was developed. The synthesis of several acyclic precursors were described, along with attempts to cyclise them. The chapter ends with the attempted synthesis of tricyclic molecules using a palladium-catalysed methodology. The last Chapter contains experimental procedures and characterisation data of all the compounds synthesised during the course of this project.