The work described in this dissertation focuses on developing copper(I) hydride (CuH)-catalyzed enantioselective hydrofunctionalization reactions of olefins. The first chapter highlights a method on CuH-catalyzed asymmetric hydroamination of strained trisubstituted alkenes, including cyclobutenes and cyclopropenes. The second chapter presents an approach for accessing enantioenriched α-quaternary carboxylic acids, through CuH-catalyzed hydrocarboxylation of allenes. The third chapter demonstrates the enantioselective hydrocarbamoylation of alkenes enable by dual CuH and Pd catalysis.Ph.D.