DescriptionEfficient catalytic methods for the transformation of C–H, O–H, and C–O bonds are key to the efficient generation of both complex molecules and commodity chemicals, and for the processing of biomass. The work presented in this dissertation attempts to address these various goals using organocatalytic and organometallic approaches. Several new types of reactions have been developed: the hydride shift-triggered C–H functionalization using a bisnucleophile, the organometallic-catalyzed intermolecular olefin hydroaryloxylation, and the atom-economic C–O bond cleavage of aryl alkyl ethers. A new type of POP pincer ligand was developed and applied to investigate pincer rhodium hydride complexes, leading to the discovery of a robust olefin isomerization catalyst.