An one-step and efficient access to the new dammarane A-quinolones by ozonolysis of 2,3-indolodipterocarpol at 0°C through the 1,3-dipolar cycloaddition of ozone to the C2-C3 double bond of the triterpenoid core is reported. In the case of oxidation in AcOH, two spiroindoles were identified as a result of 1,2-cycloaddition of ozone to the C2-C3 double bond with following intramolecular rearrangements of 2,3-epoxy-intermediate. The structures of four new compounds were established by 1H, 13C NMR, COSY, NOSY, HMBC and HSQC analyses.
McLeanJ., WattsW.E. (1960) Extractives from the Dipterocarpaceae. Journal of Organic Chemistry, 25, 1263.
2.
CrabbéP., OurissonG., TakahashiT. (1958) Le Dipterocarpol – I Préparation de la 8,14-diméthyl 18-nor-testostérone. Tetrahedron, 3, 279–302.
3.
ZorinaA.D., BalykinaL.V., NazarovaO.V., RebezovA.A. (2006) Polymeric derivatives of dipterocarpol, a dammarane triterprenoid. Russian Journal of Applied Chemistry, 79, 654–659.
4.
MillsJ.S. (1956) The constitution of the neutral, tetracyclic triterpenes of dammar resin. Journal of the Chemical Society, 189, 2196–2202.
5.
SmirnovaI.E., Do Thi ThuH., KazakovaO.B., TolstikovG.A., KukovinetsO.S., LobovA.N., SuponitskiiKYu. (2012) Ozonolysis of dipterocarpol and its derivatives. Russian Journal of Organic Chemistry, 48, 1370–1376.
6.
ThuH.D.T., TranT.T.T., TranT.H., NguenT.T., NguenQ.T., SmirnovaIE, KazakovaO.B., MinnibaevaE.M., TolstikovG.A. (2013) Synthesis and cytotoxicity of derivatives of dipterocarpol, a metabolite of Dipterocarpus alatus. Chemistry of Natural Compounds, 49, 58–65.
7.
SmirnovaI.E., KazakovaO.B., Do Thi ThuH., MinnibaevaE.M., LobovA.N., SuponitskyKYu. (2014) One-pot synthesis of hollongdione from dipterocarpol. Natural Product Communications, 9, 1417–1420.
8.
KaledinaA.S., ZorinaD.A., ZarubaevV.V., AnokhinaV.V., ErkhituevaE.V., TrifonovR.E. (2015) Synthesis and properties of 2-cyanoethoxy derivatives of dammarane triterpenoids. Russian Journal of Organic Chemistry, 51, 1627–1632.
9.
KaledinaA.S., ZorinaD.A., AnokhinaV.V., TrifonovR.E. (2015) Synthesis of tetrazol-5-ylethyl derivatives of dipterocarpol. Russian Journal of Organic Chemistry, 51, 1674–1675.
10.
AkihisaT., TokudaH., UkiyaM., SuzukiT., EnjoF., KoikeK., NikaidoT., NishinoH. (2004) 3-Epicabraleahydroxy lactone and other triterpenoids from Camellia oil and their inhibitory effects on Epstein-Barr virus activation. Chemical and Pharmaceutical Bulletin, 52, 153–156.
11.
InadaA., SomekawaM., MurataH., NakanishiT., TokudaH., NishinoH., IwashimaA., DarnaediD., MurataJ. (1993) Phytochemical studies on meliaceous plants. VIII. Structures and inhibitory effects of Epstein-Barr virus activation of triterpenoids from leaves of Chisocheton macrophyllus King. Chemical and Pharmaceutical Bulletin, 41, 617–619.
12.
PoehlandB.L., CartéB.K., FrancisT.A., HylandL.J., AllaudeenH.S., TroupeN. (1987) In vitro antiviral activity of dammar resin triterpenoids. Journal of Natural Products, 50, 706–713.
13.
AkihisaT., OgiharaJ., KatoJ., YasukawaK., UkiyaM., YamanouchiS, OishiK. (2001) Inhibitory effects of triterpenoids and sterols on human immunodeficiency virus-1 reverse transcriptase. Lipids, 36, 507–512.
14.
RévészL., HiestandP., La VecchiaL., NaefR., NaegeliH.U., ObererL., RothH.J. (1999) Isolation and synthesis of a novel immunosuppressive 17 alpha-substituted dammarane from the flour of the Palmyrah palm (Borassus flabellifer). Bioorganic and Medicinal Chemistry Letters, 9, 1521–1526.
15.
ScholzD., BaumannK., GrassbergerM., Wolff-WiniskiB., RihsG., WalterH., MeingassnerJ.G. (2004) Synthesis of dammarane-type triterpenoids with anti-inflammatory activity in vivo. Bioorganic and Medicinal Chemistry Letters, 14, 2983–2986.
16.
KazakovaO.B., Tret'yakovaE.V., KukovinetsO.S., TolstikovG.A., NazyrovT.I., ChudovI.V., IsmagilovaA.F. (2010) Synthesis and pharmacological activity of amides and the ozonolysis product of maleopimaric acid. Russian Journal of Bioorganic Chemistry, 36, 762–770.
17.
KazakovaO.B., TretyakovaE.V., KukovinetsO.S., AbdrakhmanovaA.R., KabalnovaN.N., KazakovD.V., TolstikovG.A., GubaidullinA.T. (2010) Synthesis of nontrivial quinopimaric acid derivatives by oxidation with dimethyldioxirane. Tetrahedron Letters, 51, 1832–1835.
18.
KazakovaO.B., KazakovD.V., YamansarovEYu, MedvedevaN.I., TolstikovG.A., SuponitskyKYu, ArkhipovD.E. (2011) Synthesis of triterpenoid-based 1,2,4-trioxolanes and 1,2,4-dioxazolidines by ozonolysis of allobetulin derivatives. Tetrahedron Letters, 52, 976–979.
19.
KazakovD.V., TimerbaevA.R., SafarovF.E., NazirovT.I., KazakovaO.B., IshmuratovG.Y., Terent'evA.O., BorisovD.A., TolstikovA.G., TolstikovG.A., AdamW. (2012) Chemiluminescence from the biomimetic reaction of 1,2,4-trioxolanes and 1,2,4,5-tetroxanes with ferrous ions. RSC Advances, 2, 107–110.
20.
SmirnovaI.E., ThuH.D.T., KazakovaO.B., TolstikovG.A., LobovA.N., SuponitskiiKYu. (2012) Ozonolysis of cyclomusalenone and its derivatives. Chemistry of Natural Compounds, 48, 816–820.
21.
MentelM., BreinbauerR. (2007) The Witkop-Winterfeldt-oxidation of indoles. Current Organic Chemistry, 11, 159–176.
22.
KazakovaO.B., KhusnutdinovaE.F., LobovA.N., ZverevaT.I., LegostaevaYuV, TolstikovG.A., KhrustalevV.N. (2011) Unusual ozonolysis pattern for 28-oxo-2,3-indoloallobetulin. Russian Chemical Bulletin, 60, 1781–1783.
23.
KazakovaO.B., KhusnutdinovaE.F., KorlyukovA.A. (2010) Stereospecific epoxidation of an olean-18(19)-ene-type triterpenoid. Chemistry of Natural Compounds, 46, 900–901.
24.
KhusnutdinovaE.F., MedvedevaN.I., KazakovD.V., KukovinetsO.S., LobovA.N., SuponitskyKYu, KazakovaO.B. (2016) Stereospecific oxidation of diacetoxyheterobetulin with ozone and dimethyldioxirane. Natural Product Communications, 11, 449–452.
25.
TanakaO., TanakaN., OhsawaT., IitakaY., ShibataS. (1968) Stereochemistry of the side chain of dammarane type triterpenes. Tetrahedron Letters, 40, 4235–4238.
26.
IkramA., VersianiM.A., ShamshadS., AhmedS.K., AliS.T., FaiziS. (2013) Ixorene, a new dammarane triterpene from leaves of Ixora coccinea Linn. Records of Natural Products, 7, 302–306.
