Selectivity in Organometallic Catalysis

Metal catalysis allows different modes of activity in organic reactions and transition metal catalysis strategies are highly efficient. Also the effect of it in inverse electron demand Diels-Alder (IEDDA) reactions are important for the synthesis. The mode of action for the catalyst is fully revealed and its specific effect on the regioselectivity/specificity of the reaction is established.  The silver-catalyzed IEDDA reactions of 1,2-diazines and siloxy alkynes were modeled  to highlight the effect of the catalyst and its mode of action using  Density Functional Theory (DFT). Two different reaction pathways, concerted and stepwise, were explored as well as the uncatalyzed reaction. Computations elucidate the details of the highly efficient Ag catalyst in IEDDA reaction. The uncatalyzed IEDDA reaction has also been modeled to serve as a reference point and to highlight the role of the catalyst. Natural population analysis (NPA) and frontier molecular orbitals have been analyzed to unravel how the catalyst alters the reaction kinetics and better understand the origin of the reactivity and the mechanism.