Catalytic effect of CuX (X=F, Cl, Br, I) on nitroso−Diels−Alder reaction, atheoretical study

In this study, Nitroso−Diels–Alder (NDA) cycloaddition reaction between the CH۳N=O andcis-۱,۳−butadiene in the presence of the CuX (X=F,Cl, Br, I) as Lewis acid catalyst, using densityfunctional theory calculations at the M۰۶-۲X [۱] level of theory using the def۲-svp basis set, hasbeen studied. The NDA reaction is a chemical reaction for the construction of six-membered rings[۲]. The copper(I)-catalyzed such as copper (I) and copper (II) complexes and copper salts haveused Lewis acid catalysts in Diels-Alder reactions [۳]. The aim of this work was to study varioussubstituents of X (X=F,Cl, Br, I) on the catalytic effect of the Cu catalyst in NDA cycloadditionreaction (Fig. ۱). The results showed that the largest effect on activation energies of the reactionbelongs to the CuF catalyst.The activation strain model (ASM) [۴], the quantum theory of atomsin molecules (QTAIM) and natural bond orbital (NBO) analysis were used to understand the natureof interactions at the TS structures.

Keywords:

Nitroso−Diels–Alder , CuX catalyst , DFT