A broadly applicable methodology for the regio-and enantioselective construction of branched allylic carbon-heteroatom bonds from racemic, secondary allylic trichloroacetimidates has been developed. The branched allylic substrates undergo dynamic kinetic asymmetric substitution reactions with a number of unactivated anilines and carboxylic acids as well as unactivated aromatic thiols in the presence of a chiral bicyclo[3.3.0]octadiene-ligated iridium catalyst. The allylic CÀ O, CÀ N, and CÀ S bond containing products are obtained in synthetically useful yield and selectivity. Mechanistic studies suggest that the iridium-catalyzed enantioselective substitution reactions of heteroatom nucleophiles with allylic trichloroacetimidate substrates through an outer-sphere nucleophilic addition mechanism. In addition, the chiral diene-ligated iridium catalyst is effective at promoting asymmetric aminations of acyclic secondary anilines. Importantly, this catalytic iridium methodology enables the use of alkyl substituted allylic electrophiles.