PDF herunterladen
Synlett 2006(12): 1829-1834  
DOI: 10.1055/s-2006-947356
LETTER
© Georg Thieme Verlag Stuttgart · New York

Cerium(IV) Ammonium Nitrate (CAN): A Very Efficient Reagent for the Synthesis of Tertiary Ethers

E. J. Alvarez-Manzaneda*a, R. Chabouna, E. Alvareza, E. Cabreraa, R. Alvarez-Manzanedab, A. Haidoura, J. M. Ramosa
a Departamento de Química Orgánica, Facultad de Ciencias, Instituto de Biotecnología, Universidad de Granada, 18071 Granada, Spain, +34(958)248089
e-Mail: eamr@ugr.es;
b Departamento de Química Orgánica, Facultad de Ciencias, Universidad de Almería, 04120 Almería, Spain
Weitere Informationen

Publikationsverlauf

Received 14 March 2006
Publikationsdatum:
24. Juli 2006 (online)

    Lizenzen und Reprints Alle Artikel dieser Rubrik

Abstract

Treatment of tertiary 1,4- and 1,5-diols with cerium ammonium nitrate at room temperature led to the corresponding tetrahydrofuran and tetrahydropyran derivatives in high yield and stereoselectivity. Utilizing this methodology, manoyl oxide (25a) and a variety of fragrant compounds, such as linalool oxide (8), caparrapi oxide (12), ambrox (14) and other related amber-gris-type odorants have been synthesized; 16 examples are described.

Key words

cyclizations - diols - ethers - natural products - stereo­selectivity

    References and Notes

  • Isolated from the Indian plant Coleus forskohlii. See:
  • 1a Bhat SV. Bajwa BS. Dornauer H. de Souza NJ. Fehlhaber H.-W. Tetrahedron Lett.  1977,  1669 
    CrossrefGoogle Scholar
  • 1b Bhat SV. Bajwa BS. Dornauer H. de Souza NJ. J. Chem. Soc., Perkin Trans. 1  1982,  767 
    CrossrefGoogle Scholar
  • For biological properties of 1, see:
  • 2a Bhat SV. Dohadwalla AN. Bajwa BS. Dadkar NK. Dornauer H. de Souza NJ. J. Med. Chem.  1983,  26:  486 
    CrossrefGoogle Scholar
  • 2b Khandelwal Y. Rajaswari K. Rajagopalan R. Swamy L. Dohadwalla AN. de Souza NJ. Rupp RH. J. Med. Chem.  1988,  31:  1872 
    CrossrefGoogle Scholar
  • 2c Seamon KB. Dady JW. Adv. Cyclic Nucleotide Res.  1986,  20:  1 ; and references cited therein
    CrossrefGoogle Scholar
  • For synthesis of 1, see:
  • 2d Colombo MI. Zinczuk J. Ruveda EA. Tetrahedron  1992,  48:  963 
    CrossrefGoogle Scholar
  • 2e Delpech B. Calvo D. Lett R. Tetrahedron Lett.  1996,  37:  1015 
    CrossrefGoogle Scholar
  • 3 Bhat SV. Prog. Chem. Org. Nat. Prod.  1993,  1 
    Google Scholar
  • 4 Isolated from Trypterygium wilfordii. See: Duan H. Takaishi Y. Momota H. Ohmoto Y. Taki T. Jia Y. Li D. J. Nat. Prod.  1999,  62:  1522 
    CrossrefPubMedGoogle Scholar
  • 5 Westley JW. Polyethers Antibiotics: Naturally Occurring Acid Ionophores   Vol. 1-2:  Marcel Dekker; New York: 1982. 
    Google Scholar
  • 6a Nakamura T, Oshio T, Shimizu K, and Ozawa T. inventors; JP  90-330570. 
  • 6b Nakamura M. Kunimoto S. Takahashi Y. Naganawa H. Sakane M. Inone S. Ohno T. Takeuchi T. Antimicrob. Agents Chemother.  1992,  36:  492 
    Google Scholar
  • 6c Kawada M. Sumi S. Umezawa K. Inonye S. Sawa T. Sato H. J. Antibiot.  1992,  45:  556 
    Google Scholar
  • 6d Otoguro K. Kohana A. Manabe C. Ishiyama A. Li H. Shiomi K. Yamada H. Omura S. J. Antibiot.  2001,  54:  658 
    Google Scholar
  • 7a Dobler M. Ionophores and Their Structures   John Wiley and Sons; New York: 1981. 
    Google Scholar
  • 7b Westley JW. Adv. Appl. Microbiol.  1977,  22:  177 
    Google Scholar
  • 7c Pressman BC. Annu. Rev. Biochem.  1976,  45:  501 
    Google Scholar
  • 7d Westley JW. Annu. Rep. Med. Chem.  1975,  10:  246 
    Google Scholar
  • Isolated from the culture broth of a microorganism from the genus Streptomyces. See:
  • 8a Imoto M. Umezawa K. Takahashi Y. Naganawa H. Iitaka Y. Nakamura H. Koizurni Y. Sasaki Y. Hamada M. Sawa T. Takeuchi T. J. Nat. Prod.  1990,  53:  825 
    CrossrefGoogle Scholar
  • 8b Odai H. Shindo K. Odagawa A. Mochizuki J. Hamada M. Takeuchi T. J. Antibiot.  1994,  47:  939 
    CrossrefGoogle Scholar
  • 8c Fuller NO. Morken JP. Org. Lett.  2005,  7:  4867 
    CrossrefGoogle Scholar
  • For the synthesis of cyclic ethers from diols, see:
  • 9a The Chemistry of the Hydroxyl Group, In The Chemistry of Functional Groups   Part 2:  Patai S. Interscience; London: 1971.  p.641-706  
    Google Scholar
  • 9b Comprehensive Organic Chemistry, The Synthesis and Reactions of Organic Compounds   Vol. 4:  Barton D. Ollis WD. Pergamon Press; Oxford: 1979.  p.875-877  
    Google Scholar
  • 9c Comprehensive Organic Synthesis: Selectivity, Strategy and Efficiency in Modern Organic Chemistry   Vol. 6:  Trost B. Fleming I. Pergamon; London: 1992.  p.22-31  
    Google Scholar
  • 9d Larock RC. Comprehensive Organic Transformations   John Wiley and Sons; New York: 1999.  p.89-899  
    Google Scholar
  • 9e Smith MB. March J. Advanced Organic Chemistry   Wiley Interscience; New York: 2001.  p.479-480  
    Google Scholar
  • For reviews on the use of CAN as oxidant, see:
  • 10a Richardson WH. In Oxidation in Organic Chemistry   Part A:  Wiberg KB. Academic; New York: 1965.  Chap IV.
    Google Scholar
  • 10b Ho T.-L. In Organic Syntheses by Oxidation with Metal Compounds   Mijs WJ. de Jonge CRHL. Plenum; New York: 1986.  Chap. 11.
    Google Scholar
  • 10c Handbook of Reagents for Organic Synthesis, Oxidizing and Reducing Agents   Burke SD. Danheiser RL. John Wiley and Sons; Chichester: 1999.  p.77-80  
    Google Scholar
  • 11 Mellor JM. Parkes R. Millar RW. Tetrahedron Lett.  1997,  38:  8739 
    CrossrefGoogle Scholar
  • 12 Reddy MVR. Malhotra B. Bauker YD. Tetrahedron Lett.  1995,  36:  4861 
    Google Scholar
  • 13 Ates A. Gautier A. Leroy B. Plancher J.-M. Quesnel Y. Vanherck J.-C. Markó IE. Tetrahedron  2003,  59:  8989 
    CrossrefGoogle Scholar
  • 14a Pan W.-P. Chang F.-R. Wei L.-M. Wu M.-J. Wu Y.-C. Tetrahedron Lett.  2003,  44:  331 
    CrossrefGoogle Scholar
  • 14b Goswani P. Chowdhury P. New. J. Chem.  2000,  24:  955 
    CrossrefGoogle Scholar
  • 15 Hwu JR. Jain M. Tsay S.-C. Hakimalahi GH. Tetrahedron Lett.  1996,  37:  2035 
    CrossrefGoogle Scholar
  • 16 Hwu JR. Jain M. Tasi FY. Tasy S.-C. Balakumar A. Hakimalahi GH. J. Org. Chem.  2000,  65:  5077 
    CrossrefPubMedGoogle Scholar
  • 17a Trahanovsky WS. Young MG. Nave PM. Tetrahedron Lett.  1969,  2501 
    CrossrefGoogle Scholar
  • 17b Doyle MP. Zuidema LJ. Bade TR. J. Org. Chem.  1975,  40:  1454 
    CrossrefGoogle Scholar
  • 17c Fujise Y. Kobayashi E. Tsuchida H. Ito S. Heterocycles  1978,  11:  351 
    CrossrefGoogle Scholar
  • 17d Balasubraniam V. Robinson CH. Tetrahedron Lett.  1981,  22:  501 
    CrossrefGoogle Scholar
  • 18a Trahanovsky WS. Cramer J. J. Org. Chem.  1971,  36:  1890 
    Artikel in Thieme ConnectGoogle Scholar
  • 18b Trahanovsky WS. Fox NS. J. Am. Chem. Soc.  1974,  96:  7968 
    Artikel in Thieme ConnectGoogle Scholar
  • 18c Ho T.-L. Synthesis  1978,  936 
    Artikel in Thieme ConnectGoogle Scholar
  • 19a Meyer K. Rocek J. J. Am. Chem. Soc.  1972,  94:  1209 
    CrossrefGoogle Scholar
  • 19b Hunter NR. MacAlpine GA. Liu H.-J. Valenta Z. Can. J. Chem.  1970,  48:  1436 
    CrossrefGoogle Scholar
  • 20 Trahanovsky WS. Flash PJ. Smith LM. J. Am. Chem. Soc.  1969,  91:  5068 
    CrossrefGoogle Scholar
  • 21 Trahanovsky WS. Macaulay DB. J. Org. Chem.  1973,  38:  1497 
    CrossrefGoogle Scholar
  • 22 For a review, see: Nair V. Mathew J. Prabhakaran J. Chem. Soc. Rev.  1997,  127 
    CrossrefGoogle Scholar
  • 23 For a review, see: Nair V. Panicker SB. Nair LG. George TG. Augustine A. Synlett  2003,  156 
    Artikel in Thieme ConnectGoogle Scholar
  • 24a Torii S. Uneyama K. Isihara M. J. Org. Chem.  1974,  39:  3645 
    Google Scholar
  • 24b Strikler H. Kovats E. Helv. Chim. Acta  1966,  49:  2055 
    Google Scholar
  • 25 Nakamura S. Ishihara K. Yamamoto H. J. Am. Chem. Soc.  2000,  122:  8131 ; and references cited therein
    CrossrefGoogle Scholar
  • 26 Barrero AF. Alvarez-Manzaneda EJ. Chahboun R. Paiz MC. Tetrahedron Lett.  1998,  39:  9543 ; and references cited therein
    CrossrefGoogle Scholar
  • 27a Barrero AF. Altarejos J. Alvarez-Manzaneda EJ. Ramos JM. Salido S. Tetrahedron  1993,  49:  6251 
    CrossrefGoogle Scholar
  • 27b Barrero AF. Alvarez-Manzaneda EJ. Altarejos J. Salido S. Ramos JM. Tetrahedron  1993,  49:  10405 
    CrossrefGoogle Scholar
  • 27c Barrero AF. Sánchez JF. Alvarez-Manzaneda EJ. Muñoz Dorado M. Haidour A. Tetrahedron  1994,  50:  6653 
    CrossrefGoogle Scholar
  • 27d Barrero AF. Altarejos J. Alvarez-Manzaneda EJ. Ramos JM. Salido S. J. Org. Chem.  1996,  61:  2215 ; and references cited therein
    CrossrefGoogle Scholar
  • 28 Ohloff G. Vial Ch. Demole E. Enggist P. Giersch W. Jegou E. Carus AJ. Polonsky J. Lederer E. Helv. Chim. Acta  1986,  69:  163 
    CrossrefGoogle Scholar
  • 29 Snowden RL. Eichenberger J.-C. Giersch W. Thommen W. Schulte-Elte KH. Helv. Chim. Acta  1993,  76:  1608 
    CrossrefGoogle Scholar
  • 30 Márquez C. Rodriguez González B. Valverde-López S. An. Quim.  1975,  71:  603 
    Google Scholar
  • 31 Vlad PF. Ungur ND. Synthesis  1983,  216 
    Artikel in Thieme ConnectGoogle Scholar
  • 32a Hosking JR. Brant CW. Ber. Dtsch. Chem. Ges.  1935,  68:  37 
    CrossrefGoogle Scholar
  • 32b Giles JA. Schumacher JN. Mims SS. Bernasek E. Tetrahedron  1962,  18:  169 
    CrossrefGoogle Scholar
  • 33 Conner AH. Rowe JW. Phytochemistry  1977,  16:  1777 
    CrossrefGoogle Scholar
  • 34 Coste-Manière IC. Zahra JP. Waegell W. Tetrahedron Lett.  1988,  29:  1017 
    CrossrefGoogle Scholar
35

Typical Experimental Procedure. To a deoxygenated solution of compound (1 mmol) in MeCN (10 mL) was added solid CAN (1.2 mmol) and the mixture was stirred under an argon atmosphere at r.t. for the specified time (Table [1] ). The progress of the reaction was monitored by TLC. After completion of the reaction, the solvent was removed and the residue was diluted with Et2O (20 mL), washed with H2O, brine and dried over anhyd Na2SO4. After removal of the solvent the residue was subjected to column chromatography on silica gel. Elution with 5% Et2O-hexane afforded the pure product.

36

All new compounds were fully characterized spectroscopically and had satisfactory HRMS data.
Selected data:
Compound 23: 1H NMR (400 MHz, CDCl3): δ = 1.28 (s, 3 H), 1.19 (s, 3 H), 0.85 (t, J = 3.8 Hz, 3 H), 0.85 (s, 3 H), 0.79 (s, 3 H), 0.76 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 74.6 (C), 72.9 (C), 58.3 (CH), 56.5 (CH), 43.1 (CH2), 42.2 (CH2), 39.2 (CH2), 37.9 (CH2), 36.9 (C), 35.7 (CH2), 33.4 (CH3), 33.3 (C), 27.3 (CH3), 24.9 (CH3), 21.3 (CH3), 19.9 (CH2), 18.7 (CH2), 15.8 (CH3), 15.4 (CH2), 8.1 (CH3). IR (film): 1638, 1463, 1374, 1278, 1119, 1006, 959, 845 cm-1. MS (EI) m/z (relative intensity) = 292 (3), 263 (22), 245 (100), 223 (5), 177 (18), 137 (34), 123 (23). HRMS (FAB): m/z calcd for C20H36ONa: 315.2664; found: 315.2650.
Compound 29: 1H NMR (400 MHz, CDCl3): δ = 3.90 (d, J = 10.8 Hz, 1 H), 3.72 (d, J = 10.8 Hz, 1 H), 2.06 (s, 3 H), 1.26 (s, 3 H), 1.21 (s, 3 H), 0.84 (s, 3 H), 0.77 (s, 3 H), 0.75 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 171.2 (C), 75.2 (C), 72.9 (CH2), 71.8 (C), 57.5 (CH), 56.5 (CH), 43.0 (CH2), 42.2 (CH2), 39.1 (CH2), 36.9 (C), 33.7 (CH2), 33.4 (CH3), 33.3 (C), 25.0 (CH3), 24.8 (CH3), 21.4 (CH3), 21.2 (CH3), 19.9 (CH2), 18.6 (CH2), 15.7 (CH3), 14.9 (CH3). IR (film): 1744, 1464, 1377, 1241, 1122, 1044, 994, 757 cm-1. MS (EI) m/z (relative intensity) = 336 (16), 303(7), 276 (10), 263 (12), 245 (60), 191 (10), 137 (28). HRMS (FAB): m/z calcd for C21H36O3Na: 359.2562; found: 359.2574.

Compound 31: 1H NMR (400 MHz, CDCl3): δ = 3.71 (s, 3 H), 2.13 (ddd, J = 14.0, 8.4, 4.6 Hz, 1 H), 1.85 (dt, J = 12.4, 3.3 Hz, 1 H), 1.79 (m, 2 H), 1.34 (s, 3 H), 1.22 (s, 3 H), 0.88 (dd, J = 12.5, 1.9 Hz, 1 H), 0.83 (s, 3 H), 0.76 (s, 6 H). 13C NMR (100 MHz, CDCl3): δ = 177.1 (C), 76.1 (C), 74.7 (C), 56.3 (CH), 52.4 (CH3) 52.2 (CH), 42.7 (CH2), 41.9 (CH2), 39.0 (CH2), 37.2 (C), 33.3 (CH3), 33.2 (C), 31.3 (CH2), 28.1 (CH3), 25.6 (CH3), 21.5 (CH3), 19.9 (CH2), 18.5 (CH2), 15.0 (CH3), 14.7 (CH3). IR (film): 1738, 1461, 1378, 1283, 1103, 992, 892, 849, 760 cm-1. MS (EI) m/z (relative intensity) = 323 (22), 307 (18), 263 (19), 245 (68), 196 (8), 137 (36). HRMS (FAB): m/z calcd for C20H34O3Na: 345.2406; found: 345.2412.
Compound 35: 1H NMR (400 MHz, CDCl3): δ = 3.32 (d, J = 10.6 Hz, 1 H), 3.07 (d, J = 10.6 Hz, 1 H), 2.32 (s, 1 H), 1.29 (s, 3 H), 1.16 (s, 3 H), 1.10 (dd, J = 12.6, 2.4 Hz, 1 H), 0.99 (dd, J = 12.2, 1.5 Hz, 1 H), 0.85 (s, 3 H), 0.79 (s, 3 H), 0.76 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 75.5 (C), 73.3 (C), 70.9 (CH2), 58.2 (CH), 56.4 (CH), 43.1 (CH2), 42.2 (CH2), 39.2 (CH2), 36.9 (C), 33.4 (CH3), 33.3 (C), 32.5 (CH2), 25.1 (CH3), 24.5 (CH3), 21.3 (CH3), 19.8 (CH2), 18.6 (CH2), 15.8 (CH3), 15.0 (CH3). IR (film): 3455, 1463, 1377, 1259, 1121, 1052, 960, 755 cm-1. MS (EI) m/z (relative intensity) = 294 (8), 263 (14), 245 (76), 191 (10), 149 (12), 137 (40), 83 (71). HRMS (FAB): m/z calcd for C19H34O2Na: 317.2456; found: 317.2448.