a short, efficient synthesis of (-) (3as,7as)- trans-tetrahydroactinidiolide
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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
To link to this article: http://dx.doi.org/10.1080/10575639908048482
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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: firstname.lastname@example.org 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
2 P.F. VLAD et al.
isolated from tobacco'' remained unknown because their optical rotation were not
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
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-
Acknowledgments We are gratefd to Dr. N.B.Khripach, Institute of Bioorganic
Chemistry, Belomssian Academy of Sciences, Minsk, Belorussia, for the NMR measurements.
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