Role of non-covalent interactions in catalytic asymmetric allylations and propargylations of aldehydes: Computational insights

Despite the fact that computational chemistry has become more accurate over the last ten years, non-covalent interactions continue to be a unique challenge to computational chemists. The accurate study of dispersion effects requires the use of robust correlated ab initio methods in combination with large basis sets. Finding density functional theory (DFT) methods that accurately capture the influence of non-covalent interactions in organic reactions will help decrease the computational cost as well as provide a more thorough understanding of reaction models. This work presents a study of the enantioselective allylation and propargylation reactions catalyzed by N,N-dioxides through different DFT methods (B97D, B3lLYP, M06-2x) and discusses some of the challenges faced by organic chemists when choosing  one of these methods to study a given reaction.  We also present studies of the role of non-covalent interactions in the enantioselectivity as suggested by Nakajima and coworkers in similar catalysts.