Suitability of furan, pyrrole and thiophene as dienes for Diels–Alder reactions viewed through their stability and reaction barriers for reactions with acetylene, ethylene and cyclopropene. An AM1 se.pdfVIP

Journal of Molecular Structure (Theochem) 454 (1998) 105–116 Suitability of furan, pyrrole and thiophene as dienes for Diels–Alder reactions viewed through their stability and reaction barriers for reactions with acetylene, ethylene and cyclopropene. An AM1 semiempirical and B3LYP hybrid density functional theory study Branko S. Jursic Department of Chemistry, University of New Orleans, New Orleans, LA 70148, USA Abstract The uniformity of bond orders in ?ve-membered heterocyclic compounds, Frontier Molecular Orbital (FMO) energy differences between reactants, and FMO energy changes going from reactants to transition state structures were used to evaluate the relative reactivity of furan, pyrrole, thiophene and derivatives of thiophene as dienes for Diels–Alder reactions. To determine the stereochemical outcome of these reactions, Secondary Orbital Interactions (SOI) between two reactants moieties in the isomeric transition state structures were used. All of these qualitative assessments were con?rmed through computation of the activation barriers for all possible transition state structures by AM1, B3LYP/6-31G(d)//AM1, and in some cases, by B3LYP/6-31G(d) and MP2/6-31 + G(d) methods. All observations made by combinations of various theoretical approaches were in perfect agreement with the experimental results; therefore, they are suggested as a method to be considered by synthetic organic chemists when plans for the preparation of complex organic molecules are being formulated. ? 1998 Elsevier Science B.V. All rights reserved. 1. Introduction Simple hetrocyclic compounds, e.g. furan, pyrrole and thiophene, can be structural building blocks for the preparation of a wide variety of organic compounds through their incorporation into the skeleton of the proposed organic molecule and elimination of the heteroatom [1–4]. One of the simplest ways to achieve this is through Diels–Alder reactions with the previously mentioned heterocycles as dienes [5]. After the cycloaddit