A Short, Efficient Synthesis of (-) (3as,7as)- Trans-Tetrahydroactinidiolide

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  • This article was downloaded by: [UQ Library]On: 20 November 2014, At: 09:54Publisher: Taylor & FrancisInforma Ltd Registered in England and Wales Registered Number: 1072954 Registeredoffice: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK

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    A Short, Efficient Synthesis of (-)(3as,7as)- Trans-TetrahydroactinidiolidePavel F. Vlad a , Elena C. Gorincioi a , Aculina N. Aricu a & Mihai N.Coltsa aa Institutul de Chimie al Academiei de Stiinte a Republicii Moldova ,str. Academiei 3, MD2028, Chisinu, Republic of Moldova Fax: E-mail:Published online: 04 Oct 2006.

    To cite this article: Pavel F. Vlad , Elena C. Gorincioi , Aculina N. Aricu & Mihai N. Coltsa (1999) AShort, Efficient Synthesis of (-) (3as,7as)- Trans-Tetrahydroactinidiolide, Natural Product Letters,13:1, 1-4, DOI: 10.1080/10575639908048482

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  • Natural Product Letlers Volume 13(1), pp. 1-4 Reprints available directly from the Publisher Photocopying permitted by license only

    Q 1999 OPA (Overseas Publishers Association) N.V. Published by license under

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    A SHORT, EFFICIENT SYNTHESIS OF (-) (3aS,7aS)-TMS- TETRAHYDROACTINIDIOLIDE

    Pavcl F.YLAD*, Elens C.GORINCIOI, Aculina N. ARICU and Mihai N.COLTSA

    ImtitutuI de Chimie a1 Academiei de Jtiinp a Repblicii Moldova, str. Academiei 3, Mo2028. Chi$&, Republic of Moldova

    e-mail: v~ad@terp.iciras.md F a : (373-2) 739775

    (Received 19th February 1998)

    Abstract: A short and efficient stereospedc synthesis of (-)(3aS,7aS> trans-tetrahydroactinidiolide (1) was accomplished starting with drim- 8(9)-en-7-one (4).

    Key Words: trans-tetrahydroactinidiolide, drim-8(9)-en-7-one, synthesis, ozonolysis.

    Cyclohomogeranic stereoisomeric lactones trans- and cis- tetrahydroactinidiotides (1) and (2) have been isolated from tobacco. The racemic

    lactones 1 and 2 were synthesized by several teams of re~earchers.~ These

    compounds present interest because they can be readily transformed5 into

    dihydroactinidiolide (3), an important component of hgrances of tobacco,10

    tomato, essential oils of Actinidia p~lygama,~ and Acacia farne~iana,~ as well as

    of the pheromone of the red f ie ants.6

    Strekowski and coworkers5 described the resolution of lactones 1 and 2 into

    antipodes, determined the absolute configuration of their enantiomers, and

    established the relationship between absolute configuration and the sign of optical

    rotation. It should be mentioned that the absolute configuration of lactones 1 and 2

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    isolated from tobacco'' remained unknown because their optical rotation were not

    determined.

    In this paper we report a short and efficient synthesis of (-)(3aS,7aS)-tranr- tetmhydroactinidiolide (I) starting with read@ available drimanic sesquiterpenoid

    drim-8(9)-en-7-one (4)." The latter on exhaustive omnisation in ethylacetate solution and subsequent oxidative cleavage of the ozonide with hydrogen peroxide

    have led in quantitative yield to (2-ace~l-2,6,6-trimethylcyclohexyl- 1)-acetic acid

    (5) (m.p.74.5-75.5"C (from heme-Et20); [ a ] ~ -53.9" (c 0.76, CHCb)}. Its

    structure resulted fiom spectral and microanalytical data" and fiom the obtaining

    on haloform oxidation with sodium hypobromite of the known drimic acid (6) l6 (m.p. 166.5-167.5"C; [a]~-5.7" (cl. 1, acetone)}. Lit.'? m.p. 167-168C; [a]~-7"

    (c 4.62, acetone).

    schune : a.1. 03-AcOEt, -18C; 2. 20%H2&, 70"C, 2 h., b. Br2, NaOH, dioxar~- H20 (0.3: I), r.t. 20h, reflux 15 min., c. rn-CPBA-CH& cat. c0nc.H2SO6 20"C, 48h.

    Baeyer-Williger oxidation of ketoacid 5 with rn-CPBA afforded in good yield after chromatographic purification of the reaction product on siica gel column

    directly the (-)(3aS,7aS>trans-tetrahydroactinidiolide (1) (m.p.77-78C (from

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  • A SHORT SYNTHESIS 3

    hexane); [ a ] ~ -70.7" (c 0.1, heme)). Literature data for antipode of 1' : m.p.75-

    76C ; [uID +71" (c 5, hexane ). All physical properties and spectral data of 1'' were identical with those reported in the literature.'8 Thus, under reaction conditions the primary fonned oxidation product - the acetoxy acid 7 - underwent intramolecular transestetification giving the targa compound 1.

    It is known that trum-tetrahydroactinidiolide (1) when treated with acids isomerised into thermodynamically more stable cis-lactone 2.'.1 However, under

    the reaction conditions used for Baeyer-Williger oxidation the isomerisation of

    trm-lactone 1 has not occured.

    In conclusion a short and efficient stereospecific synthesis of (-)(3aS,7aS)- trans-tetrahydroactidiolide (1) was accomplished starting with h-8(9)-en-7-

    one (4).

    Acknowledgments We are gratefd to Dr. N.B.Khripach, Institute of Bioorganic

    Chemistry, Belomssian Academy of Sciences, Minsk, Belorussia, for the NMR measurements.

    REFERENCES AND NOTES

    1. H.Kaneko, K.Hoshino (1 969) Agricultural and Biological Chemistry, 33,969 - 970.

    2. J.N.Shumacher, R.AHeckman (1971) Phyuchemistry, 10,421 - 423. 3. P.F.Vlad, N.D.Ungur, V.B.Perutsky (1991) Khim. Geterotsicl. Sotdin., 305-

    309 . (Ckm. Heteraycl. Comp., 1991. (Engl. Transl.)). 4. N.Gnonlonfoun, H.Zamarlic (1981) Tetrahehon Letters, 28,4053 - 4056. 5. L.Strekowski, M.Visnick, M.A.Battiste (1986) Journal of Organic Chemistry,

    51,4836-4839 and references cited therein.

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  • 4 P.F. VLAD er al.

    6. K.Mori, Y.Nacazono (1986) Tetrahe&on, 42,283-290.

    7. T.R.Hoye, M.J.Curth (1978) Journal of Organic Chemistry, 43, 3693 - 3697. 8. J.Briwut, R Gani, F.MuggIer-Chavan, J.P.Marion, D.Reyrnond, RH.E&

    (1 967) Helvetica Chimica Acta, 50, 1 5 1 7- 1 522.

    9. K.Ina, Y.Sacato, H.Fukami (1968) Tetrahehon Letters, 2777-2780. 10. H.Kaneko, K.Ijichi (1968) Agricultural and Biological Chemistry, 32,1337-

    1340.

    1 1. RViani, J.Bricout, J.P.Marion, F.Muggler-Chavan, D.Reymond, R.H.Egh

    (1 969) Hehtica Chimica Acta, 52, 887-89 1.

    12. T.Sacan, S.Isoe and S.B.Hyeon (1967) Tetrahedion Letters, 1623-1627.

    13. E.Demole, P.Enggist, M.Stoll(l969) Hehwtica Chimica Acta, 52,24-32.

    14. M.N.Koltsa, G.N.Mironov, S.T.Malinovskii, P.F.Vlad (1 996) Rusian Chemical Bulletin (Engl. TranS.), 45, 208-214.

    15. Compound 5 : a) IR (CC4) v- 1150, 1705 cm-' b) 'H NMR (200 M H q

    CDC13, 6 ): 0.92 [s, 6H, Ctj-(CH3h 1, 1.11 (s, 3H, C2-CH3), 2.19 (s, 3H, COCH3), 8.9 (br s, lH, COOH). Anal.Calcd for C~~HZZOJ : C, 69.02; H, 9.73. Found : C, 68.89; H, 9.62.

    16. H.H.Appe1, C.J.W.Brooks, K.H.Overton (1959) Journal of Chemical Society,

    3322-3332.

    17. Compound 1 : a) IR (nuiol) v,, 883, 914, 956, 1005, 1029, 1149, 1170, 1224,

    1241, 1767 b) 'H NMR ( 200 MHZ, CDCI3, 6 ) : 0.94 (s, 3H), 0.97 (s, 3H) [Cd-(CH3)2], 1.35 (s, 3H, C,r-CH3), 2.04 (dd, IH, J=14 and ~Hz, C3,-H), 2.30 (dd, IH, J=16.5 and ~Hz), 2.45 (dd, lH, J=16.5 and 14 Hz) (C3-CH2).

    18. ASaito, H.Matsushita, Y.Tsuino, T.Kusaki, K.Kato, M.Noguchi (1978)

    Chemzw Letters, 1065-1068.

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