Abstract: Hydrofunctionalization, which is defined as the addition of a hydrogen atom and another fragment to a degree of unsaturation, is an attractive method for transforming unsaturated hydrocarbons to value-added molecules. We developed Rh-, Pd-, and Cu-H catalysts that are capable of coupling both heteroatom and carbon nucleophiles to unsaturated hydrocarbons. The judicious choice of transition metal source (e.g., transition metal and counterion), bisphosphine ligand, and reaction conditions all play a role in selectively accessing one stereoisomeric product when many other outcomes exist.