有机化学课件-The Diels-Alder Reaction.ppt

10.12 The Diels-Alder Reaction Synthetic method for preparing compounds containing a cyclohexene ring In general... via Mechanistic features concerted mechanism cycloaddition pericyclic reaction a concerted reaction that proceeds through a cyclic transition state Recall the general reaction... The equation as written is somewhat misleading because ethylene is a relatively unreactive dienophile. What makes a reactive dienophile? The most reactive dienophiles have an electron-withdrawing group (EWG) directly attached to the double bond. Example Example Example Example Acetylenic Dienophile Diels-Alder Reaction is Stereospecific* syn addition to alkene cis-trans relationship of substituents on alkene retained in cyclohexene product Example Example Cyclic dienes yield bridged bicyclicDiels-Alder adducts. is thesame as 10.13 The p Molecular OrbitalsofEthylene and 1,3-Butadiene Orbitals and Chemical Reactions A deeper understanding of chemical reactivity can be gained by focusing on the frontier orbitals of the reactants. Electrons flow from the highest occupied molecular orbital (HOMO) of one reactant to the lowest unoccupied molecular orbital (LUMO) of the other. Orbitals and Chemical Reactions We can illustrate HOMO-LUMO interactions by way of the Diels-Alder reaction between ethylene and 1,3-butadiene. We need only consider only the p electrons of ethylene and 1,3-butadiene. We can ignore the framework of s bonds in each molecule. The p MOs of Ethylene red and blue colors distinguish sign of wave function bonding p MO is antisymmetric with respect to plane of molecule The p MOs of Ethylene LUMOHOMO The p MOs of 1,3-Butadiene Four p orbitals contribute to the p system of 1,3-butadiene; therefore, there are four p molecular orbitals. Two of these orbitals are bonding; two are antibonding. The Two Bonding p MOs of 1,3-Butadiene The Two Antibonding p MOs of 1,3-Butadiene 10.14A p Molecular Orbital Analysisof theDiels-Alder Reaction MO Analysis