Preparation and absolute configuration of (1R,4R)-(+)-3-oxo-, (1S,4S)-(-)-3-oxo- and (1R,3S,4R)-(+)-3-acetyloxy-5-oxo-1,8-cineole

Natural Product Communications

Volumn 4, Issue 11, 2009, Pages 1537-1545

  Loandos, María Del H ^a   Villecco, Margarita B ^a   Burgueño Tapia, Eleuterio ^b   Joseph Nathan, Pedro ^c   Catalán, César A N ^a  

^a UNIVERSIDAD NACIONAL DE TUCUMÁN   (Argentina)

^b INSTITUTO POLITÉCNICO NACIONAL   (Mexico)

^c DEPARTAMENTO DE FÍSICA   (Mexico)

Author keywords

(+) 3 acetyloxy 5 oxo 1,8 cineole; (+) 3 oxo 1,8 cineole; ( ) 3 oxo 1,8 cineole; Absolute configuration; Enantioselective asymmetrization; Enantioselective hydrolysis; Porcine liver esterase (PLE); Vibrational circular dichroism

Indexed keywords

1,3,3 TRIMETHYL 5 OXO 2 OXABICYCLO[2.2.2]OCTANE; 3 ACETYLOXY 1,8 CINEOLE; 3 ACETYLOXY 5 HYDROXY 1,8 CINEOLE; 3 ACETYLOXY 5 OXO 1,8 CINEOLE; 3 HYDROXY 1,8 CINEOLE; 3 OXO 1,8 CINEOLE; 3,5 DIACETYLOXY 1,8 CINEOLE; ACETIC ACID DERIVATIVE; ACETOACETIC ACID; ALCOHOL DERIVATIVE; BICYCLO[2.2.2]OCTANE DERIVATIVE; CHROMYL ACETATE; CINEOLE; ESTERASE; KETONE; PORCINE LIVER ESTERASE; SODIUM BOROHYDRIDE; UNCLASSIFIED DRUG; 3 ACETYLOXY 5 OXO 1 ,8 CINEOLE; 3-ACETYLOXY-5-OXO-1 ,8-CINEOLE; DYES, REAGENTS, INDICATORS, MARKERS AND BUFFERS; TERPENE;

ARTICLE; CHROMATOGRAPHY; CIRCULAR DICHROISM; DENSITY FUNCTIONAL THEORY; DRUG ACETYLATION; DRUG HYDROLYSIS; DRUG OXIDATION; ENANTIOMER; ENANTIOSELECTIVITY; RACEMIC MIXTURE; REDUCTION; CHEMISTRY; CONFORMATION; MASS FRAGMENTOGRAPHY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; OXIDATION REDUCTION REACTION; PH; STEREOISOMERISM;

SUS;

CIRCULAR DICHROISM; GAS CHROMATOGRAPHY-MASS SPECTROMETRY; HYDROGEN-ION CONCENTRATION; INDICATORS AND REAGENTS; MAGNETIC RESONANCE SPECTROSCOPY; MOLECULAR CONFORMATION; MONOTERPENES; OXIDATION-REDUCTION; STEREOISOMERISM;

EID: 75549083331     PISSN: 1934578X     EISSN: 15559475     Source Type: Journal    
DOI: 10.1177/1934578x0900401116     Document Type: Article

References (51)

1. (a) Abbott P, Abbott T. (2005) Eucalyptus oil: Australia's Natural Wonder. Felton Grimwade & Bickford Pty Ltd., Melbourne;
2. (b)Harborne JB, Baxter H (eds) (1993) Phytochemical Dictionary, A Handbook of Bioactive Compounds from Plants. Taylor and Francis, London;
3. (c) Zrira S, Bessiere JM, Menut C, Elamrani A, Benjilali B. (2004) Chemical composition of the essential oil of nine Eucalyptus species growing in Morocco. Flavour and Fragrance Journal, 19, 172-175;
4. (d) Bignell CM, Dunlop PJ, Brophy JJ, Jackson JF (1996) Volatile leaf oil of some South-westerrn and Southern Australian Species of the Genus Eucalyptus. Part XII. A. Subgenus Eudesmia: B. Subgenus Symphyomyrtus: Section Exsertaria; Series Globulares. Flavour and Fragrance Journal, 11, 145-151;
5. (e) Gûenther E. (1949) The Essential Oils. Van Nostrand Reinhold Co. New York, vol. II, 708.
6. (a) Laude EA, Morice AH, Grattan TJ. (1994) The antitussive effects of menthol, camphor and cineole in conscious guinea-pigs. Pulmonary Pharmacology, 7, 179-184;
7. (b) Tzakou O, Pitarokilli D, Chinou IB, Harvala C. (2001) Composition and antimicrobial activity of the essential oil of Salvia ringens. Planta Medica, 67, 81-83;
8. (c) Coppen JW. (2002) Production, trade and markets for eucalyptus oils. In Eucalyptus: The genus Eucalyptus, Medicinal and Aromatic Plants-Industrial Profiles, vol. 22, Coppen JW (Ed). Taylor & Francis, London;
9. (d) Miyazawa M, Shindo M, Shimada T. (2001) Oxidation of 1,8-cineole, the monoterpene cyclic ether originated from Eucalyptus polybractea, by cytochrome P450 3A enzymes in rat and human liver microsomes. Drug Metabolism and Disposition, 29, 200-205. (Pubitemid 32112936)
10. Simonsen JL. (1953) The Terpenes. Cambridge University Press, Vol 1, 423-432.
11. Silvestre AJD, Cavaleiro JAS. (1996) 1,8-Cineole: applications, metabolism and chemical transformations. Revista Farmacéutica, 138, 49-57.
12. De Martinez MV, De Venditti FG, De Fenik IJS, Catalán, CAN. (1982) Oxidation of 1,8-cineole with chromyl acetate. Some new oxygenated derivatives of 1,8-epoxy-p-menthane. Journal of the Argentine Chemical Society, 70, 137-148.
13. De Boggiatto MV, De Heluani CS, De Fenik IJS, Catalán CAN. (1987) Regiospecific functionalization of the monoterpene ether 1,3,3-trimethyl-2- oxabicyclo[2.2.2]octane (1,8-cineole). Synthesis of the useful bridged γ-lactone 1,3-dimethyl-2-oxabicyclo[2.2.2]octan-3→5-olide. Journal of Organic Chemistry, 52, 1505-1511.
14. Villecco MB, Muro AC, Catalán, JV, Catalán CAN. (2005) Capítulo IX. Síntesis de derivados de 1,8-cineol, cariofileno y cariolan-1-ol con utilidad en perfumería y farmacología. In Plantas Iberoamericanas como fuente de terpenoides útiles en química fina. A. Fernández Barrero (Ed). ISBN 84-96023-32-x Programa CYTED, Granada, Spain, 189-211.
15. (a) Mac Rae IA, Alberts V, Carman RM, Shaw IM. (1979) Products of 1,8-cineole oxidation by a Pseudomonas. Australian Journal of Chemistry, 32, 917-922;
16. (b) Carman RM, MacRae IC, Perkins MV. (1986) The oxidation of 1,8-cineole by Pseudomonas flava. Australian Journal of Chemistry, 39, 1739-1746;
17. (c) Liu WG, Rosazza JPN. (1990) Stereospecific hydroxylation of 1,8-cineole using a microbial catalyst. Tetrahedron Letters, 31, 2833-2836;
18. (d) Trudgill PW. (1990) Microbial metabolism of monoterpenes-recent developments. Biodegradation, 1, 93-105;
19. (e) Rasmussen JAM, Henderson KA, Straffon MJ, Dumsday GJ, Coulton J, Zachariou M. (2005) Two new biocatalysts for improved biological oxidation of 1,8-cineole. Australian Journal of Chemistry, 58, 912-916.
20. (a) Southwell IA. (1975) Essential oil metabolism in the koala. III Novel urinary monoterpenoid lactones. Tetrahedron Letters, 24, 1885-1888;
21. (b) Boyle R, McLean S, Foley W, Davies NW, Peacock EJ, Moore B. (2001) Metabolites of dietary 1,8-cineole in the male koala (Phascolarctos cinereus). Comparative Biochemistry and Physiology Part C, 129, 385-395;
22. (c) Boyle R, McLean S, Davies NW. (2000) Biotransformation of 1,8-cineole in the brushtail opossum (Trichosurus vulpecula). Xenobiotica, 30, 915-932;
23. (d) Flynn TM, Southwell IA. (1979) 1,3-Dimethyl-2-oxabicyclo[2.2.2] octane-3-methanol and 1,3-Dimethyl-2-oxabicyclo[2.2.2] octane-3-carboxylic acid, urinary metabolites of 1,8-cineole. Australian Journal of Chemistry, 32, 2093-2095;
24. (e) Miyazawa M, Kameoka H, Morinaga K, Negoro K, Mura N. (1989) Hydroxycineole: four new metabolites of 1,8-cineole in rabbits. Journal of Agricultural and Food Chemistry, 37, 222-226.
25. Bitteur, SM, Baumes RL, Bayonove CL, Versini G, Martin CA, Dalla Serra A. (1990) 2-exo-Hydroxy-1,8-cineole: A new component from grape var. Sauvignon. Journal of Agricultural and Food Chemistry, 38, 1210-1213.
26. Southwell IA, Russel MF, Maddox CDA, Wheeler GS. (2003) Differential metabolism of 1,8-cineole in insects. Journal of Chemical Ecology, 29, 83-94.
27. Duisken M, Sandner F, Blömeke B, Hollender J. (2005) Metabolism of 1,8-cineole by human cytochrome P450 enzymes: Identification of a new hydroxylated metabolite. Biochimica et Biophysica Acta, 1722, 304-311. (Pubitemid 40354168)
28. Rodriguez P, Sierra W, Rodriguez S, Menendez P. (2006) Biotransformation of 1,8-cineole, the main product of Eucalyptus oils. Electronic Journal of Biotechnology, 9, 232-236. (Pubitemid 44033402)
29. Williams RD, Trudgill PW, Taylor DG. (1989) Metabolism of 1,8-cineole by Rhodococcus species: Ring cleavage reactions. Journal of General Microbiology, 135, 1957-1967.
30. (a) Kubota K, Nakamura K, Kobayashi A. (1998) Acetyloxy-1,8-cineoles as aroma constituents of Alpinia galanga Willd. Journal of Agricultural and Food Chemistry, 46, 5244-5247; (Pubitemid 128488290)
31. (b) Kubota K, Someya Y, Yoshida R, Kobayashi A, Morita T, Koshino H. (1999) Enanatiomeric purity and odor characteristics of 2- and 3-acetyloxy-1,8-cineoles in the rhizomes of Alpinia galanga Willd. Journal of Agricultural and Food Chemistry, 47, 685-689;
32. (c) Miyasawa M, Hashimoto Y. (2002) Antimicrobial and bactericidal activities of esters of 2-endo-hydroxy-1,8-cineole as new aroma chemicals. Journal of Agricultural and Food Chemistry, 50, 3522-3526.
33. Luzzio FA, Duveau DY. (2002) Enzymatic resolution of the 1,3,3-trimethyl-2-oxabicyclo[2.2.2]octane (1,8-cineole) system. Tetrahedron Asymmetry, 13, 1173-1180.
34. Loandos MH, Muro AC, Villecco MB, Catalán CA. (2006) Stereospecificity of pig liver esterase in the hydrolysis of racemic esters derived from 1,8-cineole. Molecular Medicinal Chemistry, 10, 35-37.
35. (a) Perdew JP. (1986) Density-functional approximation for the correlation energy of the inhomogeneous electron gas. Physical Reviews B, 33, 8822-8824;
36. (b) Godbout N, Salahud DR, Andzelm J, Wimmer E. (1992) Optimization of Gaussian-type-basis sets for local spin functional calculations. Part 1. Boron through neon, optimization technique and validation. Canadian Journal of Chemistry, 70, 560-571;
37. (c) Andzelm J, Wimmer EJ. (1992) Density functional Gaussian-type-orbital approach to molecular geometries, vibrations, and reaction energies. Journal of Chemical Physics, 96, 1280-1303.
38. Because the peaks of the enantiomeric acetates (+)-4 and (-)-4 are not baseline resolved, chiral GC quantization below 1.5% could not be done as the peak of the minor enantiomer is swallowed by the much larger peak of the major enantiomer. On the other hand, a very accurate enantiomer quantization could be made on enantiomeric ketones (+)- and (-)-2 as they were nicely resolved giving acute and baseline-separated peaks.
39. Dale JA, Mosher HS. (1973) Nuclear magnetic resonance enantiomer reagents. Configurational correlations via nuclear magnetic resonance chemical shifts of diastereoisomeric mandelate, O-methylmandelate, and α-methoxy-α-trifluoromethylphenylacetate (MTPA) esters. Journal of the American Chemical Society, 95, 512-519.
40. Preite MD. (1994) Determinación de excesos enantioméricos y asignación de configuraciones absolutas por análisis de resonancia magnética nuclear. Química Nova, 17, 137-151.
41. Chang G, Guida WC, Still WC. (1989) An internal-coordinate Monte Carlo method for searching conformational space. Journal of the American Chemical Society, 111, 4379-4386.
42. (a) Halgren T. (1996) Merck molecular force field. I. Basis, form, scope, parameterization, and performance of MMFF94, Journal of Computational Chemistry, 17, 616-641;
43. (b) Halgren TA. (1996) Merck molecular force field. II. MMFF94 van der Waals and electrostatic parameters for intermolecular interactions. Journal of Computational Chemistry, 17, 587-615;
44. (c) Halgren TA. (1996) Merck molecular force field. III. Molecular geometries and vibrational frequencies for MMFF94. Journal of Computational Chemistry, 17, 553-586;
45. (d) Halgren TA. (1996) Merck molecular force field. V. Extension of MMFF94 using experimental data, additional computational data, and empirical rules. Journal of Computational Chemistry, 17, 490-519.
46. (a) Godbout N, Salahud DR, Andzelm J, Wimmer E. (1992) Optimization of Gaussian-type-basis sets for local spin functional calculations. Part 1. Boron through neon, optimization technique and validation. Canadian Journal of Chemistry, 70, 560-571.
47. (b) Andzelm J, Wimmer EJ. (1992) Density functional Gaussian-type-orbital approach to molecular geometries, vibrations, and reaction energies. Journal of Chemical Physics, 96, 1280-1303.
48. (a) Rojas-Pérez R, Cedillo-Portugal E, Joseph-Nathan P, Burgueño-Tapia E. (2009) A new longipine diester from Stevia monardifolia Kunth. Natural Product Communications, 4, 757-762;
49. (b) Muñoz MA, Areche C, San-Martín A, Rovirosa J, Joseph-Nathan P. (2009) VCD determination of the absolute configuration of stypotriol. Natural Product Communications, 4, 1037-1040.
50. Villecco MB, Hernández LR, Guzmán MI, Catalán CAN, Bucio MA, Joseph-Nathan P. (2001) Synthesis, stereochemistry and absolute configuration of deodarols and deodarones. Tetrahedron Asymmetry, 12, 2947-2953.
51. Villecco MB, Catalán JV, Vega MI, Garibotto FM, Enriz RD, Catalán CAN. (2008) Synthesis and antibacterial activity of highly oxygenated 1,8-cineole derivatives. Natural Product Communications, 3, 303-312.