Triterpenoids with a β-ketonitrile group in five-membered ring A were synthesized via intramolecular oxonitrile cyclization of C-3 methyl esters of 1-cyano-substituted 2,3-seco-triterpene acids. The intramolecular cyclization to form the triterpene ketonitriles and subsequent reduction of the oxo groups to give C-1 and C-3 substituents in the β-orientation were confirmed to be stereoselective. Alkaline hydrolysis of the ketonitriles reduced the cyano groups to form the corresponding 3-oxo-2-nor-derivative while reduction and acylation of the β-hydroxynitrile formed an α,β-alkenenitrile fragment in the triterpenoid five-membered ring A.
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Acknowledgment
The work was financially supported by State Task No. AAAA-A18-118030790037-7. We thank the Common Use Center of PFRC, UrB, RAS, “Research of Materials and Compounds” for spectral and analytical studies and Dr. M. V. Dmitriev, Sr. Scientist of Perm State National Research University, for the XSA of 8.
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Translated from Khimiya Prirodnykh Soedinenii, No. 6, November–December, 2020, pp. 933–938.
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Tolmacheva, I.A., Igosheva, E.V., Eltsov, O.S. et al. Synthesis and Transformation of Triterpenoids with a β-Ketonitrile Fragment in Five-Membered Ring A. Chem Nat Compd 56, 1088–1093 (2020). https://doi.org/10.1007/s10600-020-03233-6
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DOI: https://doi.org/10.1007/s10600-020-03233-6