Reactions catalyzed by organic catalysts (amines, amino acids and amino alcohols) are often plagued by low reactivity (high catalyst loadings and long reaction times) and limited substrate scope. In order to overcome these limitations, we decided to investigate the highly nucleophilic trialkylphosphines as organocatalysts in order to facilitate the design of new synthetic organic methodologies. We envisaged that phosphines would provide superior reactivity due to their enhanced polarizability at phosphorus relative to analogous nitrogen centered catalysts. As part of our program of studies towards the development of new organocatalyzed reactions involving phosphonium enolates we initially sought to develop an efficient methodology for the dimerization of ketoketenes. This reaction would facilitate the study of the reaction of phosphines with ketenes, and furthermore provide a rare opportunity to study the reactivity of phosphonium enolate species. The mild nucleophilicity of the more commonly used ammonium enolate systems often stymies the development of new reactions or limits the substrate scope of these methodologies. We envisaged that a new chiral phosphine system would supersede previous systems through the superior nucleophilicity displayed by phosphines, and the accordant enhanced nucleophilicity of derived phosphonium enolates relative to ammonium enolates. The expected superior reactivity of the phosphonium enolates should lead to the development of new reactions involving less reactive electrophiles (ketoketenes, ketones and ketimines as electrophilic partners). The anticipated discovery of a successful catalytic asymmetric phosphine system for ketoketene dimerization would have great relevance for all catalytic [2+2]-cycloadditions involving ketoketenes, with the promise of a general system for all reactions of ketoketenes involving ammonium/phosphonium enolate intermediates. The synthetic utility of the proposed methodology will be validated through its application to the synthesis of interesting drug molecules (LY426965, a novel fungicide, and (-)-phenserine).