Abstract
The reactions of (3S,4RS)-1,3-dideoxy-3-[(2Z)-4-methoxy-3-methyl-4-oxobut-2-en1-yl]-4-C-methyl-4,5-O-(1-methylethylidene)pent-2-ulose with MCPBA and trifluoroperacetic acid were studied. It was shown that 60% MCPBA in CH2Cl2 at room temperature caused isomerization in the acetonide fragment of this compound, while no expected Baeyer—Villiger (B—V) reaction was observed at the methyl ketone. In the MCPBA—AcONa system, the epoxidation of the activated double bond followed the conjugate addition—elimination scheme. The oxidation with trifluoroperacetic acid occurred at the methyl ketone moiety with subsequent decomposition of the dioxolane protecting group and intramolecular lactonization. The introduction into the B—V reaction of the corresponding aldehyde-containing partner instead of the methyl ketone-containing ulose led to an abnormal product of furanization with the loss of the chiral center.
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Acknowledgments
The spectroscopic part of the study and theoretical calculations were carried out using the equipment of the Center for Collective Use “Chemistry” of the Ufa Institute of Chemistry, Ural Federal Research Center of the Russian Academy of Sciences.
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The work was carried out in the framework of the Russian state assignment No. 122031400261-4.
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Dedicated to the memory of Academician of the Russian Academy of Sciences G. A. Tolstikov (1933–2013).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, Vol. 72, No. 10, pp. 2392–2398, October, 2023.
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Sunagatullina, G.R., Khursan, S.L., Lobov, A.N. et al. Features of the Baeyer—Villiger reaction in the case of a complex variously functionalized substrate. Russ Chem Bull 72, 2392–2398 (2023). https://doi.org/10.1007/s11172-023-4038-0
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DOI: https://doi.org/10.1007/s11172-023-4038-0