2-Aminoalkylgold Complexes: The Putative Intermediate in Au-Catalyzed Hydroamination of Alkenes Does Not Protodemetalate

Au-catalyzed hydroamination proceeds well for alkynes but not alkenes. We report gas-phase binding energies of alkenes and alkynes to a cationic Au center, which indicate that differences in binding are not the origin of the disparate chemical behavior. We further report the synthesis and characterization of 2-aminoalkylgold complexes, which would be the intermediates in a hypothetical Au-catalyzed hydroamination of styrene. The reactivity of the well-characterized and isolable complexes reveals that protonation or alkylation of the 2-aminoalkylgold complexes results in amine elimination in solution, and in the gas phase, indicating that the failure of Au-catalyzed alkene hydroamination derives from a non-competitive protodeauration step. We analyze possible transition states for the protodeauration, and identify an insufficiently strong Au-proton interaction as the reason that the transition states lie too high in energy to compete.

Automated summary

Au-catalyzed hydroamination is successful for alkynes but not alkenes. Gas-phase binding energy studies suggest that differences in binding are not responsible for the different chemical behavior. The synthesis and characterization of 2-aminoalkylgold complexes reveal that protonation or alkylation leads to amine elimination, indicating that a non-competitive protodeauration step is responsible for the failure of Au-catalyzed alkene hydroamination.