Abstract: Hydrofunctionalizations are an attractive method for functionalizing olefins, forging new bonds in an atom-economic and sustainable fashion. We developed a variety of Rh–H catalysts that can couple heteroatom nucleophiles with olefin coupling partners.. In the first example, we developed an intermolecular anti-Markovnikov hydroamination of 1,3-dienes to form homoallylic amines. In the second example, we developed a divergent hydrothiolation of cyclopropenes.