| Summary: | Chapter One reviews the literature, discussing the application of metallocarbenoids in asymmetric synthesis. This introduction is mainly concerned with asymmetric carbon-carbon and carbon-heteroatom bond forming reactions and pays particular attention to the levels of stereoselectivity that have been achieved. Chapter Two discusses the use of novel homochiral rhodium(II) carboxylates to effect asymmetric induction in a range of carbenoid transformations. The preparation of these novel rhodium(II) carboxylates is discussed, together with their application in asymmetric catalysis. The work presented is particularly concerned with the insertion of rhodium carbenoids into the heteroatom-hydrogen bond of alcohols, thiols, amines and silanes to prepare enantiomerically enriched a-substituted esters. Chapter Three discusses the generation of oxygen and sulfur ylides followed by a [2,3] sigmatropic rearrangement to generate enantiomerically enriched esters containing a quaternary chiral centre. Asymmetric cyclopropanations and carbon-hydrogen insertion reactions are also discussed. Chapter Four examines the use of diazo phosphonoacetate in organic synthesis. The work has concentrated on the preparation of N-substituted aminophosphonoacetates, by the insertion reactions of anilines, amides and carbamates. These compounds have then been manipulated to prepare a series of amino esters and peptides.
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