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Synthetic transformations of higher terpenoids: XVII. Intramolecular cyclization of N-furfuryl amides of the labdane series

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Abstract

16-(Benzylaminomethyl)lambertianic acid methyl ester reacts with 2-methylprop-2-enoyl chloride to give unsaturated amide which readily undergoes intramolecular [4 + 2]-cycloaddition with formation of terpenoid derivatives of 10-oxa-3-azatricyclo[5.2.1.01,5]decenone. Acetylation of lambertianic acid methyl ester with acetic anhydride occurs preferentially at the 2-position of the furan ring and is accompanied by migration of the exocyclic double bond. Reductive amination of 16-acetyl-15,16-epoxylabda-8(9),13,14-triene and subsequent reaction of the resulting amine with 2-methylprop-2-enoyl chloride give intramolecular cyclization products in high yield without isolation of intermediate furfurylacryloyl derivative. Reactions of methyl 16-(benzylaminomethyl)-15,16-epoxylabda-8(9),13,14- and -8(17),13,14-trien-18-oates with maleic anhydride lead to the formation of the corresponding 10-oxa-3-azatricyclo[5.2.1.01,5]dec-8-ene-6-carboxylic acid derivatives as mixtures of diastereoisomers.

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Authors and Affiliations

  1. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences, pr. Akademika Lavrent’eva 9, Novosibirsk, 630090, Russia

    Yu. V. Kharitonov, E. E. Shul’ts, M. M. Shakirov & G. A. Tolstikov

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  1. Yu. V. Kharitonov
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  2. E. E. Shul’ts
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  3. M. M. Shakirov
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  4. G. A. Tolstikov
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Correspondence to Yu. V. Kharitonov.

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Original Russian Text © Yu.V. Kharitonov, E.E. Shul’ts, M.M. Shakirov, G.A. Tolstikov, 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 4, pp. 521–528.

For communication XVI, see [1].

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Kharitonov, Y.V., Shul’ts, E.E., Shakirov, M.M. et al. Synthetic transformations of higher terpenoids: XVII. Intramolecular cyclization of N-furfuryl amides of the labdane series. Russ J Org Chem 44, 516–523 (2008). https://doi.org/10.1134/S1070428008040088

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  • DOI: https://doi.org/10.1134/S1070428008040088

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