Dra. Durán-Guajardo, Rocío

In this article, we present a comprehensive computational investigation into the reaction mechanism of N-arylation of substituted aryl halides through Ullmann-type coupling reactions. Our computational findings, obtained through DFT ωB97X-D/6-311G(d,p) and ωB97X-D/LanL2DZ calculations, reveal a direct relation between the previously reported experimental reaction yields and the activation energy of haloarene activation, which constitutes the rate-limiting step in the overall coupling process. A detailed analysis of the reaction mechanism employing the Activation Strain Model indicates that the strain in the substituted iodoanilines is the primary contributor to the energy barrier, representing an average of 80% of the total strain energy. Additional analysis based on conceptual Density Functional Theory (DFT) suggests that the nucleophilicity of the nitrogen in the lactam is directly linked to the activation energies. These results provide valuable insights into the factors influencing energetic barriers and, consequently, reaction yields. These insights enable the rational modification of reactants to optimize the N-arylation process.

In this paper, we will study the reactivity along with substituent changes in the OH insertion reaction in copper carbenoids. To this end, we have used M06-2X functional with cc-pVDZ for light atoms and LanL2DZ for copper. We have studied the IRC insertion profiles and analysed reactivity indexes such as electrophilicity (ω) and pKa calculations. We have found that with R1 substitutions phenyl group, R2 substitutions amide group lower the reaction barrier considerably. Concerning the substrate reactions, the most favoured substituent is NO2 in para position.