Homogeneous gold(I) catalysis, a field of study relatively unexplored as recently as 1998, has rapidly become a vital synthetic tool for the activation of carbon multiple bonds.  Unlike many transition metal catalysts which might have 4 or more ligands, gold(I) is 2-coordinate.  This means that catalysts utilizing gold(I) can only bear a single ligand, as the other site must be available for the substrate to bind.  For this reason a gold(I) catalyst’s reactivity is highly dependent upon the chosen ligand.  Recently, bidentate P,N ligands have begun to be utilized as their pendant amine group serves as an additional site where reactivity and selectivity can be tuned.  As examples of exceptional reactivity from this class of ligands become more numerous, the need for a theoretical framework explaining the origins and limitations of these effects becomes more pressing.  A series of novel P,N ligands was synthesized with the intention of probing the effect of the pendant amine groups on the catalytic enhancement observed among catalysts bearing these types of ligands.  The intramolecular hydroalkoxylation of 3-Pentynol was used as a test reaction in order to quantify each catalyst’s effectiveness and the influence of amine position and basicity on pi-activation and protodeauration.  Reaction progress and initial rates were observed using Nuclear Magnetic Resonance Spectroscopy.  Catalysts and reaction intermediates were characterized by NMR spectroscopy and single crystal X-Ray diffraction.      <br/>

Synthesis and mechanistic exploration of novel P,N-ligated gold(I) compounds:  Effect of pendant amine groups on catalytic enhancement

253rd National Meeting (2017)

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