A reexamination of the molecular mechanism of the Diels–Alder reaction between tetrafluoroethene and cyclopentadiene

Abstract

DFT calculation results shed a new light on the mechanism of cycloaddition reaction between tetrafluoroethene and cyclopentadiene. The unique influence of fluorine atoms on the ethylene derivative molecule causes the [2 ? 2] cycloaddition process to take place according to a stepwise, biradical mechanism. At the same time, the competitive and independent path leads to a one-step (and not a twostep, as was once thought) cycloaddition reaction leading to a [2 ? 4] cycloadduct.

Kinetics, Thermodynamics, and Theoretical Studies in a Diels‐Alder Dimerization Process of 3‐Vinylindole Derivative of the 3‐Indoleacetic Acid: An Auxin.

“…Thus, DAR should be classified as non‐polar (N‐DAR), where synchronical, one‐step or two‐steps (which is less common), biradical mechanism are possible. Polar (P‐DAR) are also possible where they are characterized as asynchronical, stepwise, zwitterionic mechanism processes . In order to classify the DAR as N‐DAR or P‐DAR, the Global Electron Density Transfer (GEDT) values were used.…”

A quantum‐chemical DFT study of the mechanism and regioselectivity of the 1,3‐dipolar cycloaddition reaction of nitrile oxide with electron‐rich ethylenes

“…In this part, we have investigated the nature of the molecular mechanism of these 13DC reactions. Is it occurring through a two‐stage one‐step mechanism or one‐stage one‐step mechanism …”

Investigation of the reaction mechanism of [4 + 2] cyclization of 2,3 dimethylbuta-1,3-diene to methylacrylate using the Michaelis-Menten equation

“…It was appropriate to examine in more detail the mechanism of this reaction. Note that the mechanism of the [4 +2]-cycloaddition reaction today is still controversial [7].…”