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Activation Of Propargylic Alcohols By Piano-Stool Ruthenium Complexes Bearing Phosphoramidite Ligands, Stephen Andrew Costin

Dissertations

Various piano-stool ruthenium complexes bearing phosphoramidite ligands have been synthesized and characterized spectroscopically and in some cases structurally. Reaction of phosphoramidite ligands with an appropriate metal precursor gives new piano-stool ruthenium complexes [RuCl(L)(arene)(phosphoramidite)], where L = Cl, PPh3, or others. The novel complexes are tested for their ability to activate propargylic alcohols catalytically as well as stoichiometrically. Specifically, catalytic substitution of propargylic alcohols via allenylidene intermediates is envisioned. Stoichiometric reactions designed to form stable, isolable allenylidenes are sought as well. h6-p-cymene complexes of the type [RuCl2(h6-p-cymene)(phosphoramidite)] activate propargylic alcohols in the reaction with carboxylic acids to form b-oxo esters. The …