Abstract
Base-catalyzed rearrangements of both individual 4-(acylmethylidene)butenolides and their mixtures prepared by condensation of citraconic anhydride with various phosphoranes occur successfully only in the presence of 5.2% MeONa in MeOH (molar ratio MeONa: substrate ≤ 10: 1, room temperature, 1–2 h). Under these conditions, the yields of 2-cinnamoyl-4-methylcyclopent-4-ene-1,3-dione (coruscanone B) and 2-acetyl-4-methylcyclopent-4-ene-1,3-dione are 56 and 65%, respectively. With a considerable increase in the reaction temperature or the molar ratio MeONa: substrate, formal addition of MeOH to the C(4)=C(5) double bond of these triketones becomes an appreciable (or predominant) process. A reaction of coruscanone B with CH2N2 in ether gives coruscanone A as a ~3: 2 mixture of (Z)- and (E)-methyl enolates (43%); other products (10%) result from the expansion and aromatization of the five-membered ring of the triketone. The simplest analog of coruscanone B, 2-acetyl-4-methylcyclopent-4-ene-1,3-dione, reacts with CH2N2 in a similar way.
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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 82–91, January, 2010.
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Shestak, O.P., Novikov, V.L. Synthesis of coruscanones A and B, metabolites of Piper coruscans, and related compounds. Russ Chem Bull 59, 81–90 (2010). https://doi.org/10.1007/s11172-010-0048-9
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DOI: https://doi.org/10.1007/s11172-010-0048-9