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Synthesis 2010(22): 3855-3864  
DOI: 10.1055/s-0030-1258265
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

3-Alkoxy-2,5-dihydrofurans by Gold-Catalyzed Allenyl Cyclizations and Their Transformation into 1,4-Dicarbonyl Compounds, Cyclopentenones, and Butenolides

Malte Brasholz, Branislav Dugovič, Hans-Ulrich Reissig*
Institut für Chemie und Biochemie, Freie Universität Berlin, Takustr. 3, 14195 Berlin, Germany
Fax: +49(30)83855367; e-Mail: hans.reissig@chemie.fu-berlin.de;
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Publication History

Received 7 July 2010
Publication Date:
24 September 2010 (online)

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Abstract

The addition of lithiated alkoxyallenes to carbonyl compounds furnishes allenyl alcohols, which undergo a highly efficient and chemoselective 5-endo-trig cyclization to 3-alkoxy-2,5-dihydrofurans catalyzed by gold(I) chloride. The dihydrofurans produced can be either oxidized to β-alkoxy butenolides by a manganese(III) acetate catalyzed radical oxidation with tert-butyl hydroperoxide, or transformed into α,β-unsaturated γ-keto aldehydes by an oxidative ring cleavage using DDQ in the presence of water. Treatment of the γ-keto aldehydes with sodium methoxide in methanol promotes a diastereoselective intramolecular aldol addition furnishing alkoxy-substituted cyclopentenone derivatives in good yield.

Key words

allenes - dihydrofurans - cyclopentenones - gold catalysis - allylic oxidation

    References

  • For reviews, see:
  • 1a Zimmer R. Synthesis  1993,  165 
    Google Scholar
  • 1b Zimmer R. Reissig H.-U. In Modern Allene Chemistry   Vol. 1:  Krause N. Hashmi ASK. Wiley-VCH; Weinheim: 2004.  p.425-492  
    Google Scholar
  • 1c Brasholz M. Reissig H.-U. Zimmer R. Acc. Chem. Res.  2009,  42:  45 
    Google Scholar
  • 1d Pfrengle F. Reissig H.-U.  Chem. Soc. Rev.  2010,  39:  549 
    Google Scholar
  • 2 Hormuth S. Reissig H.-U. J. Org. Chem.  1994,  59:  67 ; references 8 and 9
    CrossrefGoogle Scholar
  • 3a Okala Amombo MG. Hausherr A. Reissig H.-U. Synlett  1999,  1871 
    Google Scholar
  • 3b Breuil-Desvergnes V. Compain P. Vatèle J.-M. Goré J. Tetrahedron Lett.  1999,  40:  5009 
    Google Scholar
  • 3c Breuil-Desvergnes V. Compain P. Vatèle J.-M. Goré J. Tetrahedron Lett.  1999,  40:  8789 
    Google Scholar
  • 3d Breuil-Desvergnes V. Goré J. Tetrahedron  2001,  57:  1939 
    Google Scholar
  • 3e Breuil-Desvergnes V. Goré J. Tetrahedron  2001,  57:  1951 
    Google Scholar
  • 3f Flögel O. Okala Amombo MG. Reissig H.-U. Zahn G. Brüdgam I. Hartl H. Chem. Eur. J.  2003,  9:  1405 
    Google Scholar
  • 3g Kaden S. Brockmann M. Reissig H.-U. Helv. Chim. Acta  2005,  88:  1826 
    Google Scholar
  • 3h Kaden S. Reissig H.-U. Org. Lett.  2006,  8:  4763 
    Google Scholar
  • 3i Chowdhury MA. Reissig H.-U. Synlett  2006,  2383 
    Google Scholar
  • 4a Schade W. Reissig H.-U. Synlett  1999,  632 
    Google Scholar
  • 4b Helms M. Schade W. Pulz R. Watanabe T.
    Al-Harrasi     A. Fišera L. Hlobilová I. Zahn G. Reissig H.-U. Eur. J. Org. Chem.  2005,  1003 
    Google Scholar
  • 5a Flögel O. Dash J. Brüdgam I. Hartl H. Reissig H.-U. Chem. Eur. J.  2004,  10:  4283 
    Google Scholar
  • 5b Dash J. Lechel T. Reissig H.-U. Org. Lett.  2007,  9:  5541 
    Google Scholar
  • 5c Lechel T. Dash J. Hommes P. Lentz D. Reissig H.-U. J. Org. Chem.  2010,  75:  726 
    Google Scholar
  • 6 Gwiazda M. Reissig H.-U. Synthesis  2008,  990 
    Article in Thieme ConnectGoogle Scholar
  • 7 Lechel T. Lentz D. Reissig H.-U. Chem. Eur. J.  2009,  15:  5432 
    CrossrefGoogle Scholar
  • 8 Hoff S. Brandsma L. Arens JF. Recl. Trav. Chim. Pays-Bas  1969,  88:  609 
    Google Scholar
  • 9 Brasholz M. Reissig H.-U. Synlett  2007,  1294 
    Article in Thieme ConnectGoogle Scholar
  • 10 For a review, see: Kilroy TG. O’Sullivan TP. Guiry PJ. Eur. J. Org. Chem.  2005,  4929 
    CrossrefGoogle Scholar
  • 11 For an example, see: Donohoe TJ. Helliwell M. Stevenson CA. Tetrahedron Lett.  1998,  39:  3071 
    CrossrefGoogle Scholar
  • Selected examples:
  • 12a Ozawa F. Kubo A. Hayashi T. Tetrahedron Lett.  1992,  33:  1485 
    Google Scholar
  • 12b Pearce AJ. Ramaja S. Thorn SN. Bloomberg GB. Walter DS. Gallagher T. J. Org. Chem.  1999,  64:  5453 
    Google Scholar
  • 12c Glorius F. Tetrahedron Lett.  2003,  44:  5751 
    Google Scholar
  • 13 For an example, see: Guindon Y. DeLorme D. Lau CK. Zamboni R. J. Org. Chem.  1988,  53:  267 
    CrossrefGoogle Scholar
  • Selected examples:
  • 14a Baylon C. Heck MP. Mioskowski C. J. Org. Chem.  1999,  64:  3354 
    Google Scholar
  • 14b Heck MP. Baylon C. Nolan SP. Mioskowski C. Org. Lett.  2001,  13:  1989 
    Google Scholar
  • 14c Duffy MG. Grayson DH. J. Chem. Soc., Perkin Trans. 1  2002,  1555 
    Google Scholar
  • 15 For an example, see: Barry CN. Evans SA. J. Org. Chem.  1983,  48:  2825 
    CrossrefGoogle Scholar
  • Reviews of furan chemistry:
  • 16a König B. In Science of Synthesis   Vol. 9:  Maas G. Thieme; Stuttgart: 2002.  p.183-285  
    Google Scholar
  • 16b Brown RCD. Angew. Chem. Int. Ed.  2005,  44:  850 ; Angew. Chem. 2005, 117, 872
    Google Scholar
  • 16c Senning A. Wong HNC. Yeung K.-S. Yang Z. Graening T. Thrun F. Keay BA. Hopkins JM. Dibble PW. In Comprehensive Heterocyclic Chemistry III   Katritzky AR. Ramsden CA. Scriven EFC. Taylor RJK. Elsevier; Amsterdam: 2008. 
    Google Scholar
  • 17 Bailey PS. Christian JD. J. Am. Chem. Soc.  1949,  71:  4122 
    CrossrefGoogle Scholar
  • 18 Raczko J. Tetrahedron  2003,  59:  10181 
    CrossrefGoogle Scholar
  • 19a Antonioletti R. Arista L. Bonadies F. Locati L. Scettri A. Tetrahedron Lett.  1993,  34:  7089 
    Google Scholar
  • 19b Yang ZC. Zhou W.-S. J. Chem. Soc., Perkin Trans. 1  1994,  3231 
    Google Scholar
  • 19c Finlay J. McKervey MA. Gunaratne HQN. Tetrahedron Lett.  1998,  39:  5651 
    Google Scholar
  • 19d Massa A. Acocella MR. De Rosa M. Soriente A. Villano R. Scettri A. Tetrahedron Lett.  2003,  44:  835 
    Google Scholar
  • 20a Piancatelli G. Scettri A. D’Auria M. Tetrahedron Lett.  1977,  18:  2199 
    Google Scholar
  • 20b Piancatelli G. Scettri A. D’Auria M. Tetrahedron  1980,  36:  661 
    Google Scholar
  • 20c Antonioletti R. D’Auria M. De Mico A. Piancatelli G. Scettri A. Synthesis  1984,  280 
    Google Scholar
  • 21 Georgiadis MP. Couladouros EA. J. Org. Chem.  1986,  51:  2725 
    CrossrefGoogle Scholar
  • 22 Lefevre Y. Tetrahedron Lett.  1972,  13:  133 
    CrossrefGoogle Scholar
  • 23 For a review, see: Knight DW. Contemp. Org. Synth.  1994,  1:  287 
    CrossrefGoogle Scholar
  • For reviews, see:
  • 24a Zografos AL. Georgiadis D. Synthesis  2006,  3157 
    Google Scholar
  • 24b Schobert R. Schlenk A. Bioorg. Med. Chem.  2008,  16:  4203 
    Google Scholar
  • 25a Shono T. Matsumura Y. Yamane S. Tetrahedron Lett.  1981,  22:  3269 
    Google Scholar
  • 25b Kuwajima I. Urabe H. Tetrahedron Lett.  1981,  22:  5191 
    Google Scholar
  • 25c Pelter A. Rowlands M. Tetrahedron Lett.  1987,  28:  1203 
    Google Scholar
  • 26a Flögel O. Reissig H.-U. Eur. J. Org. Chem.  2004,  2797 
    Google Scholar
  • 26b Brasholz M. Reissig H.-U. Angew. Chem. Int. Ed.  2007,  46:  1634 ; Angew. Chem. 2007, 119, 1659
    Google Scholar
  • 26c Brasholz M. Reissig H.-U. Eur. J. Org. Chem.  2009,  3595 
    Google Scholar
  • 26d Dugovič B. Reissig H.-U. Synlett  2008,  769 
    Google Scholar
  • 27a Krause N. Laux M. Hoffmann-Röder A. Tetrahedron Lett.  2000,  41:  9613 
    Google Scholar
  • 27b Berry CR. Hsung RP. Antoline JE. Petersen ME. Challepan R. Nielson JA. J. Org. Chem.  2005,  70:  4038 
    Google Scholar
  • 28a Olsson L.-I. Claesson A. Synthesis  1979,  743 
    Google Scholar
  • 28b Marshall JA. Wang X.-J. J. Org. Chem.  1990,  55:  2995 
    Google Scholar
  • 29a Hoffmann-Röder A. Krause N. Org. Lett.  2001,  3:  2537 
    Google Scholar
  • 29b Krause N. Hoffmann-Röder A. Canisius J. Synthesis  2002,  1759 
    Google Scholar
  • 29c Hoffmann-Röder A. Krause N. Org. Biomol. Chem.  2005,  3:  387 
    Google Scholar
  • 30 Beaulieu PL. Morisset VM. Tetrahedron Lett.  1980,  21:  129 
    CrossrefGoogle Scholar
  • 31 Magnus P. Albaugh-Robertson P. J. Chem. Soc., Chem. Commun.  1984,  804 
    CrossrefGoogle Scholar
  • 32 Flögel O. Ph.D. Dissertation   Freie Universität Berlin; Germany: 2003. 
    Google Scholar
  • Selected reviews:
  • 33a Hashmi ASK. Angew. Chem. Int. Ed.  2005,  44:  6990 ; Angew. Chem. 2005, 117, 7150
    Google Scholar
  • 33b Hashmi ASK. Hutchings GJ. Angew. Chem. Int. Ed.  2006,  45:  7896 ; Angew. Chem. 2006, 118, 8064
    Google Scholar
  • 33c Hashmi ASK. Chem. Rev.  2007,  107:  3180 
    Google Scholar
  • 33d Bongers N. Krause N. Angew. Chem. Int. Ed.  2008,  47:  2178 ; Angew. Chem. 2008, 120, 2208
    Google Scholar
  • 34 Gockel B. Krause N. Org. Lett.  2006,  8:  4485 
    CrossrefPubMedGoogle Scholar
  • 35a

    Our results have shown that the addition of lithiated alkoxyallenes to α-chiral aldehydes predominantly proceeds via the Felkin-Anh mode in all cases (also see ref. 2). Assignment of syn- and anti-isomers was based on NMR data for most compounds, at the stage of the allenyl alcohol intermediates, and according to guidelines by Landmann and Hoffmann.

  • 35b Landmann B. Hoffmann RW. Chem. Ber.  1987,  120:  331 
    Google Scholar
  • 35c

    The assignment for compound 4d could be confirmed by an X-ray analysis of the main isomer.

  • 35d Brasholz M. Ph.D. Dissertation   Freie Universität Berlin; Germany: 2007. 
    Google Scholar
  • 36a Corey EJ. Fleet GWJ. Tetrahedron Lett.  1973,  4499 
    Google Scholar
  • 36b Salmond WG. Barta MA. Havens JL. J. Org. Chem.  1978,  43:  2057 
    Google Scholar
  • 37 Marco JA. Carda M. Rodríguez S. Castillo E. Kneeteman MN. Tetrahedron  2003,  59:  4085 
    CrossrefGoogle Scholar
  • 38 Sayama S. Inamura Y. Heterocycles  1996,  43:  1371 
    CrossrefGoogle Scholar
  • 40 Achmatowicz O. Bukowski P. Szechner B. Zwierzchowska Z. Zamojki A. Tetrahedron  1971,  27:  1973 
    CrossrefGoogle Scholar
  • For reviews, see:
  • 41a Holder NL. Chem. Rev.  1982,  82:  287 
    Google Scholar
  • 41b Harris JM. Li M. Scott JG. O’Doherty GA. In Strategies and Tactics in Organic Synthesis   Vol. 5:  Harmata M. Elsevier; London: 2004.  p.221-253  
    Google Scholar
  • 43 Shing TKM. Yeung Y.-Y. Su PL. Org. Lett.  2006,  8:  3149 
    CrossrefGoogle Scholar
  • 44a Yu J.-Q. Corey EJ. J. Am. Chem. Soc.  2003,  125:  3232 
    Google Scholar
  • 44b Yu J.-Q. Wu H.-C. Corey EJ. Org. Lett.  2005,  7:  1415 
    Google Scholar
  • 45 Meister C. Scharf H.-D. Synthesis  1981,  737 
    Article in Thieme ConnectGoogle Scholar
  • 46 Li C. Nitka MV. Gloer JB. J. Nat. Prod.  2003,  66:  1302 
    CrossrefGoogle Scholar
  • 47 Omura K. Swern D. Tetrahedron  1978,  34:  1651 
    CrossrefGoogle Scholar
  • 48 Pérez M. Canoa P. Gómez G. Teijeira M. Fall Y. Synthesis  2005,  411 
    Article in Thieme ConnectGoogle Scholar
  • 49a Massad SK. Hawkins LD. Baker DC. J. Org. Chem.  1983,  48:  5180 
    Google Scholar
  • 49b Smith ND. Kocienski PJ. Street S. Synthesis  1996,  652 
    Google Scholar
39

This was demonstrated for closely related compounds, see refs. 26b, 26c.

42

Attempted asymmetric organocatalytic variants of the reaction have so far been unsuccessful.