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

摘要

The addition of O-H and N-H bonds across carbon-carbon double bonds offers a direct wayudof synthesising a variety of organic molecules. These reactions have attracted considerableudinterest in academic research and the chemical/pharmaceutical industry in recent years dueudto its atom economy. Nevertheless, there remains a considerably challenge to control theudregioselectivity and the stereoselectivity of this reaction.udThis PhD thesis describes the investigation into the discovery and development of a generaludmethod for catalytic hydroamination (HA), hydroalkoxylation and hydrooxyacylation ofudolefins. Air- and moisture-stable transition metal catalysts were the main focus of thisudstudy.udThe introductory Chapter provides an overview of recent advances in N-H additionudreactions involving late transition metal catalysts.udIn Chapter 2, rhodium and ruthenium complexes were examined as catalysts for theudaddition of N-H bonds to alkenes. The combination of (RuCl2)n/dppb/AgOTf generated audcatalyst effective for the addition of methyl carbamate to norbornene in a modest yield.udCopper (II) trifluoromethanesulfonate was discovered to be an efficient catalyst for theudaddition of carboxylic acids, phenols and alcohols to norbornene. A selection of norbornyludesters and ethers were formed in good to excellent yields.udIn the following Chapter, the combination of copper (II) trifluoromethanesulfonate anduddiphosphine ligands was successfully applied to the addition of sulfonamides andudcarbamates to vinylarenes, 1,3-dienes and norbornene in good to excellent yields.udIn Chapter 4, the intramolecular hydroamination reaction was developed. The synthesis ofudseveral acyclic precursors were described, along with attempts to cyclise them. The chapterudends with the attempted synthesis of tricyclic molecules using a palladium-catalysedudmethodology.udThe last Chapter contains experimental procedures and characterisation data of all theudcompounds synthesised during the course of this project.