The first general synthesis of 1-substituted [3]dendralenes has led to the discovery that conjugating groups significantly enhance the rate of Diels-Alder dimerisation relative to both the parent [3]dendralene and to other substituted systems.

A rare example of the application of a catalytic, enantioselective Diels-Alder cycloaddition to affect a kinetic resolution has been developed. Chiral pyrazolidinones are resolved with high selectivity through a process that utilizes a relay of stereochemical information from a permanent chiral center to a fluxional chiral center to enhance the inherent selectivity of the chiral Lewis acid cata...

Alder±ene reactions are a powerful way to construct carbon±carbon bonds. The intramolecular version of these reactions can provide efficient routes to produce a variety of heterocyclic and carbocyclic compounds.[1] Since the thermal Alder±ene reaction requires high temperature, it has found limited applications in organic syntheses. In contrast, transition-metal-catalyzed Alder±ene reactions ca...

Controlled isomerization of the double bond of certain Diels-Alder reactions provides substrates that, upon oxidation, give rise to products whose gross structure corresponds to that of a Robinson annulation. In these cases, the stereochemistry of the Robinson annulation product reflects the fact that the initial combination occurred in a Diels-Alder mode. Using these principles, we have synthe...

The amino acid proline catalyzed the three- and five-component cascade olefination-Diels-Alder-epimerization and olefination-Diels-Alder-epimerization-olefination-hydrogenation reactions of readily available precursors enones 1a-i, arylaldehydes 2a-k, alkyl cyanoacetates 3a-e and Hantzsch ester 9 to furnish highly substituted prochiral 1-cyano-4-oxo-2,6-diaryl-cyclohexanecarboxylic acid alkyl e...

Synthesis of 2,3- and 3,4-cyclopentenopyridines, 5,6,7,8-tetrahydroquinolines and 5,6,7,8-tetrahydroisoquinolines from 1,2,4-triazine derivatives is reported. Introduction of an alpha-functionalized methyl substituent (e.g. arylsulphonyl, sulphonamide, sulphonic acid ester) into position 3- or 6- of triazines by vicarious nucleophilic substitution of hydrogen and subsequent alkylation with alky...

The electron-reorganization along the concerted and stepwise pathways associated with the non-polar Diels-Alder reaction between cyclopentadiene (Cp, 1) and ethylene (2) has been studied using the topological analysis of the electron localization function (ELF) at the B3LYP/6-31G(d) level of theory. ELF results for the concerted mechanism stresses that the electron-reorganization demanded on th...