Total synthesis and proof of relative stereochemistry of (-)-aureonitol

Journal of Organic Chemistry

Volumn 73, Issue 19, 2008, Pages 7616-7624

  Jervis, Peter J ^a   Cox, Liam R ^a  

^a UNIVERSITY OF BIRMINGHAM   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDES; ARSENIC COMPOUNDS; CHEMICAL REACTIONS; CHEMISTRY; CHLORINE COMPOUNDS; CYCLIZATION; ORGANIC COMPOUNDS; RAW MATERIALS; STEREOCHEMISTRY;

CHEMICAL EQUATIONS; CYCLIZATION REACTIONS; DIASTEREOISOMER; INTRAMOLECULAR ALLYLATION; NATURAL PRODUCTS; REDUCTION SEQUENCES; STEREO-SELECTIVE; TETRA-HYDROFURAN; TETRAHYDROFURANS; TOTAL SYNTHESIS;

COMPLEXATION;

ALDEHYDE; ALLYLSILANE; AUREONITOL; NATURAL PRODUCT; SILANE DERIVATIVE; TETRAHYDROFURAN; TETRAHYDROFURAN DERIVATIVE; UNCLASSIFIED DRUG;

ALLYLATION; ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CHAETOMIUM; CYCLIZATION; HELICHRYSUM; PROTON NUCLEAR MAGNETIC RESONANCE; STEREOCHEMISTRY; SYNTHESIS;

ANTI-BACTERIAL AGENTS; BIOLOGICAL PRODUCTS; CYCLIZATION; FUNGI; FURANS; MAGNETIC RESONANCE SPECTROSCOPY; MOLECULAR STRUCTURE; OXIDATION-REDUCTION; STEREOISOMERISM;

EID: 53049106166     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo801338t     Document Type: Article

References (54)

1. Bohlmann, F.; Ziesche, J. Phytochemistry 1979, 18, 664-665.
2. Helichrysum aureonitens is a hairy perennial herb that grows in the Kwazulu-Natal province of South Africa. It belongs to a large genus of about 500 species. According to folklore, it has been used for centuries by the people of this province against infection. In 1995, Meyer (Meyer, J. J. M.; Afolayan, A. J. J. Ethnopharmacol. 1995, 47, 109-111.) found that the dichloromethane extract of H. aureonitens was active against a wide range of gram-positive bacteria, yet inactive against all gram-negative bacteria tested (including Escherichia coli).
3. Burrows, B. F. J. Chem. Soc., Chem. Commun. 1967, 597.
4. Chaetomium spp. are filamentous fungi found in soil, air, and plant debris. As well as being a contaminant, Chaetomium spp. are also causative agents of infections in humans. The Chaetomium genus contains over 100 species, with the most common being C. atrobrunneum, C. funicola, C. globosum, and C. strumarium.
5. Mason, S. F.; Vane, G. W. J. Chem. Soc., Chem. Commun. 1967, 598.
6. (a) Seto, H.; Saito, M.; Uzawa, J.; Yonehara, H. Heterocycles 1979, 13, 247-253.
7. (b) Saito, M.; Seto, H.; Yonehara, H. Agric. Biol. Chem. 1983, 47, 2935-2937.
8. Abraham, W. R.; Arfmann, H. A. Phytochemistry 1992, 31, 2405-2408.
9. Teuscher, F. Ph.D. thesis, Heinrich-Heine-Universität, Germany, 2005.
10. (a) Beignet, J.; Jervis, P. J.; Cox, L. R. J. Org. Chem. 2008, 73, 5462-5475.
11. (b) Ramalho, R.; Jervis, P. J.; Kariuki, B. M.; Humphries, A. C.; Cox, L. R. J. Org. Chem. 2008, 73, 1631-1634.
12. (c) Jervis, P. J.; Kariuki, B. M.; Cox, L. R. Tetrahedron Lett. 2008, 49, 2514-2518.
13. (d) Jervis, P. J.; Cox, L. R. Beilstein J. Org. Chem. 2007, 3, 6.
14. (e) Jervis, P. J.; Kariuki, B. M.; Cox, L. R. Org. Lett. 2006, 8, 4649-4652.
15. (f) Ramalho, R.; Beignet, J.; Humphries, A. C.; Cox, L. R. Synthesis 2005, 3389-3397.
16. (g) Simpkins, S. M. E.; Kariuki, B. M.; Aricó, C. S.; Cox, L. R. Org. Lett. 2003, 5, 3971-3974.
17. (h) Beignet, J.; Cox, L. R. Org. Lett. 2003, 5, 4231-4234.
18. Activation of the ring oxygen could potentially result in the opening of the tetrahydrofuran ring at C-2 to generate a stabilized pentadienyl cation.
19. (a) Goubert, M.; Toupet, L.; Sinibaldi, M. E.; Canet, I. Tetrahedron 2007, 63, 8255-8266.
20. (b) Yokokawa, F.; Inaizumi, A.; Shioiri, T. Tetrahedron Lett. 2001, 42, 5903-5908.
21. Fischer, E.; Speier, A. Chem. Ber. 1895, 28, 3252-3258.
22. Confirmation that no loss of stereochemical integrity had occurred along the synthetic sequence was confirmed by chiral HPLC analysis of 18 and comparison with a racemic sample (see the Supporting Information).
23. (a) Dewi, P.; Randl, S.; Blechert, S. Tetrahedron Lett. 2005, 46, 577-580.
24. (b) Funk, T. W.; Efskind, J.; Grubbs, R. H. Org. Lett. 2005, 7, 187-190.
25. (c) Moura-Letts, G.; Curran, D. P. Org. Lett. 2007, 9, 5-8.
26. Chatterjee, A. K.; Choi, T.-L.; Sanders, D. P.; Grubbs, R. H. J. Am. Chem. Soc. 2003, 125, 11360-11370.
27. A sealed tube was employed owing to the volatility of diene 19 (bp 42°C).
28. Metathesis catalyst 20 and 21 were provided by Dr. David Lindsay, University of Reading, UK.
29. (a) Yamamoto, K.; Ohta, O.; Tsuji, J. Chem. Lett. 1979, 713-716.
30. (b) Tucker, J. R.; Riley, D. P. J. Organomet. Chem. 1985, 279, 49-62.
31. (c) Crousse, B.; Alami, M.; Linstrumelle, G. Tetrahedron Lett. 1997, 38, 5297-5300.
32. (d) Tuckett, M. W.; Watkins, W. J.; Whitby, R. J. Tetrahedron Lett. 1998, 39, 123-126.
33. (a) Hoffmann, R. W.; Schäfer, F.; Haeberlin, E.; Rohde, T.; Körber, K. Synthesis 2000, 2060-2068.
34. (b) Burgess, E. M.; Penton, H. R., Jr.; Taylor, E. A. J. Org. Chem. 1973, 38, 26-31.
35. (c) Burgess, E. M.; Penton, H. R., Jr.; Taylor, E. A. J. Am. Chem. Soc. 1970, 92, 5224-5226.
36. (d) Atkins, G. M.; Burgess, E. M. J. Am. Chem. Soc. 1968, 90, 4744-4745.
37. (a) VanRheenen, V.; Kelly, R. C.; Cha, D. Y. Tetrahedron Lett. 1976, 1973-1976.
38. (b) Betancort, J. M.; Martin, T.; Palazon, J. M.; Martin, V. S. J. Org. Chem. 2003, 68, 3216-3224.
39. Yu, W.; Mei, Y.; Kang, Y.; Hua, Z.; Jin, Z. Org. Lett. 2004, 6, 3217-3219.
40. Wang, Y.; West, F. G. Synthesis 2002, 99-103.
41. (a) Sodeoka, M.; Yamada, H.; Shibasaki, M. J. Am. Chem. Soc. 1990, 112, 4906-4911.
42. (b) Bestmann, H. J.; Süss, J.; Vostrowsky, O. Liebigs Ann. Chem. 1981, 2117-2138.
43. (a) Blakemore, P. R. J. Chem. Soc., Perkin Trans. 1 2002, 2563-2585.
44. (b) Blakemore, P. R.; Cole, W. J.; Kocienski, P. J.; Morley, A. Synlett 1998, 26-28.
45. (c) Kocienski, P. J.; Bell, A.; Blakemore, P. R. Synlett 2000, 365-366.
46. Takano, D.; Nagamitsu, T.; Ui, H.; Shiomi, K.; Yamaguchi, Y.; Masuma, R.; Kuwajima, I.; Ōmura, S. Org. Lett. 2001, 3, 2289-2291.
47. (a) Paterson, I.; Steven, A.; Luckhurst, C. A. Org. Biomol. Chem. 2004, 2, 3026-3038.
48. (b) Adger, B. J.; Barrett, C.; Brennan, J.; McGuigan, P.; McKervey, M. A.; Tarbit, B. J. Chem. Soc., Chem. Commun. 1993, 1220-1222.
49. (a) Chattopadhyay, S. K.; Pattenden, G. J. Chem. Soc., Perkin Trans. 1 2000, 2429-2454.
50. (b) Crouch, R. D. Tetrahedron 2004, 60, 5833-5871.
51. The ratio of (E,E)-33:(E,Z)-33 improved from 4:1 to 5:1 after purification by column chromatography.
52. Brinza, I. M.; Fallis, A. G. J. Org. Chem. 1996, 61, 3580-3581.
53. 3OD.
54. Marwah, R. G.; Fatope, M. O.; Deadman, M. L.; Al-Maqbali, Y. M.; Husband, J. Tetrahedron 2007, 63, 8174-8180.