Intramolecular Diels-Alder Reactions of α-Bromostyrene-Functionalized Unsaturated Carboxamides.

Intramolecular cycloaddition reactions of α-bromostyrene-functionalized amides of monomethyl fumarate were investigated. The reaction of the amides with Et3N in toluene at 110 °C gave 1,4-dihydronaphthalenes. The 1,4-dihydronaphthalenes may be produced via the intramolecular Diels-Alder reaction, proton transfer, and dehydrobromination by a base, along with C═C bond isomerization by proton transfer. The reaction of amide derivatives with halogen on a benzene ring and alkali metal carbonates in toluene at 110 °C gave naphthalene derivatives directly. Dehydrogenation of various 1,4-dihydronaphthalenes with cesium or rubidium carbonate in toluene at 110 °C gave naphthalene derivatives. The retardation by TEMPO, acceleration by air for some substrates, and density functional theory calculations suggest a radical mechanism caused by intervention of molecular oxygen.