The Nitrilimine–Alkene Cycloaddition Regioselectivity Rationalized by DensityFunctional Theory Reactivity Indices

Molecules

Giorgio Molteni¹  Alessandro Ponti² 

[1] Dipartimento di Chimica, Università degli Studi di Milano, via C. Golgi 19, 20133 Milano, Italy;Istituto di Scienze e Tecnologie Molecolari, Consiglio Nazionale delle Ricerche, via C. Golgi 19, 20133 Milano, Italy;

关键词: 1,3-dipolar cycloaddition;    nitrilimine;    alkene;    regioselectivity;    conceptual density functional theory;    reactivity indices;    softness;   

DOI  :  10.3390/molecules22020202

来源: DOAJ

【 摘 要 】

Conventional frontier molecular orbital theory is not able to satisfactorily explain the regioselectivity outcome of the nitrilimine–alkene cycloaddition. We considered that conceptual density functional theory (DFT) could be an effective theoretical framework to rationalize the regioselectivity of the title reaction. Several nitrilimine–alkene cycloadditions were analyzed, for which we could find regioselectivity data in the literature. We computed DFT reactivity indices at the B3LYP/6-311G(2d,p)//B3LYP/6-31G(d,p) and employed the grand potential stabilization criterion to calculate the preferred regioisomer. Experimental and calculated regioselectivity agree in the vast majority of cases. It was concluded that predominance of a single regioisomer can be obtained by maximizing (i) the chemical potential difference between nitrilimine and alkene and(ii) the local softness difference between the reactive atomic sites within each reactant.Such maximization can be achieved by carefully selecting the substituents on both reactants.

【 授权许可】

Unknown