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AlkoxyalleneâBased LANCA ThreeâComponent Synthesis of 1,2âDiketones, Quinoxalines, and Unique Isoindenone Dimers and a Computational Study of the Isoindenone Dimerization
A series of βâalkoxyâβâketoenamides was prepared by the wellâestablished LANCA threeâcomponent reaction of lithiated 1â(2âtrimethylsilylethoxy)âsubstituted allenes, nitriles, and Îą,βâunsaturated carboxylic acids. The Îąâtertâbutylâsubstituted compounds were smoothly converted into the expected 1,2âdiketones by treatment with trifluoroacetic acid. A subsequent condensation of the 1,2âdiketones with oâphenylenediamine provided the desired highly substituted quinoxalines in good overall yield. Surprisingly, the Îąâphenylâsubstituted βâalkoxyâβâketoenamides investigated afford not only the expected 1,2âdiketones, but also pentacyclic compounds with an antiâtricyclo[4.2.1.12,5]decaâ3,7âdieneâ9,10âdione core. These interesting products are very likely the result of an isoindenone dimerization which was mechanistically studied with the support of DFT calculations. Under the strongly acidic reaction conditions, a stepwise reaction is likely leading to a protonated isoindenone as reactive intermediate. It may first form a van der Waals complex with a neutral isoindenone before the two regioâ and diastereoselective ring forming steps occur. Interestingly, two neutral or two protonated isoindenones are also predicted to dimerize giving the observed pentacyclic product
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