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Synthetic Transformations of Higher Terpenoids. XXXIII.* Preparation of 15,16-Dihydroisopimaric Acid and Methyl Dihydroisopimarate and their Transformations

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Methods were proposed for preparing 15,16-dihydroisopimaric acid and its methyl ester. Oxidation of methyl dihydroisopimarate through the action of 3-chloroperbenzoic acid occurred with formation of 7,8-epoxy-derivatives and 7α-hydroxydihydrosandaracopimarate. The latter in addition to 7-oxotetrahydroisopimarate were formed through the action of t-butylhydroperoxide in the presence of MoCl5. Oxidation of dihydroisopimaric acid or the ester by selenium dioxide in dioxane gave the corresponding 14α-hydroxy-derivatives. Pyridinium chlorochromate transformed 14α-hydroxydihydroisopimarate into a mixture of methyl esters of 7α-hydroxy-8,14-epoxyisopimaric, 7-oxo-8,14-epoxyisopimaric, 7-oxo-14-hydroxyisopimaric, and 7α-hydroxysandaracopimaric acids. Oximation of methyl 7-oxotetrahydroisopimarate by hydroxylamine hydrochloride in MeOH in the presence of NaOAc gave a mixture of the corresponding (Z)- and (E)-oximes. Beckmann rearrangement of the 7-(E)-oxime of methyl tetrahydroisopimarate through the action of thionylchloride led to tetradecahydrodibenzo[b,d]azepine.

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Acknowledgment

The work was supported financially by RFBR grant No. 12-03-00535.

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Authors and Affiliations

  1. N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, 630090, Novosibirsk, Prosp. Lavrent’eva, 9, Russia

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

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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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Correspondence to E. E. Shul’ts.

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Translated from Khimiya Prirodnykh Soedinenii, No. 6, November–December, 2013, pp. 916–923.

* For No. XXXII, see the literature [1].

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Kharitonov, Y.V., Shul’ts, E.E. & Shakirov, M.M. Synthetic Transformations of Higher Terpenoids. XXXIII.* Preparation of 15,16-Dihydroisopimaric Acid and Methyl Dihydroisopimarate and their Transformations. Chem Nat Compd 49, 1067–1075 (2014). https://doi.org/10.1007/s10600-014-0823-1

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