Copper hydride (CuH) has been shown to enable a number of selective 1,2- and 1,4-reductions when complexed with the appropriate ligand, yet the allylic substitution chemistry of CuH has been much less studied. This dissertation describes the further study of CuH to perform sequential reductions on Morita-Baylis-Hillman (MBH) adducts. Specifically: I) Selectivity in the SN2 reduction of MBH adducts was shown to be highly dependant on the nature of the ligand used. II) The reaction of MBH alcohols was shown to involve an initial dehydrogenative silylation with PMHS, where both the oligomeric nature and electronics of the initially formed trialkoxysilyl ether intermediate are important in determining both the observed stereoselectivity, and efficiency of the substitution. III) MBH ketones could be employed in tandem SN2/1,2-reduction sequences to arrive at stereodefined allylic alcohols with central chirality. Vinylsilanes are versatile intermediates in organic synthesis owing to numerous methods for their transformation into other functional groups that proceed with high stereoretention. While there are numerous methods to synthesize stereodefined vinylsilanes from alkynes, many existing methods require the use of highly reactive moisture intolerant reagents and harsh reaction conditions, features that limit the functionality that can be accommodated. Even fewer of these existing methods are conducted under environmentally responsible conditions. The use of Suginomes reagent as a moisture tolerant source of nucleophilic silicon, small catalytic quantities of a simple copper(I) salt, and an aqueous solution of TPGS-750-M as an environmentally benign nonionic surfactant, is described herein as a highly effective combination of reagents that allows for the stereoselective silylcupration of conjugated alkynes giving access to a variety of (E)--silyl-substituted carbonyl derivatives under environmentally responsible conditions. This dissertation also describes the application of substituted allenoates as electrophilic butadienyl coupling partners under palladium catalysis in aqueous micellar media. The substituted allenoates could then be transformed by the methods developed herein into a variety of 2-substituted butadienes, where the methods were then extended to provide entry into a variety of substituted [3]-[6]dendralenes. Specifically: I) Application of an additive based screen allowed for evaluation of functional group tolerance in the Pd-catalyzed coupling of substituted allenoates with boronic acids. II) Curiosity driven investigations to identify boron based sp3 coupling reagents compatible with the conditions of micellar catalysis led to the identification of OBBD alkylborinate reagents as stable and isolable coupling reagents, which was the applied to the synthesis of 2-alkyl 1,3-butadienes. III) An analogous vinylallenyl coupling partner that functions formally as an electrophilic [3]dendralene synthon was proposed, and a number of synthetic routes were