Download PDF
Synthesis 2005(2): 311-329  
DOI: 10.1055/s-2004-834879
FEATUREARTICLE
© Georg Thieme Verlag Stuttgart · New York

New Method for the Synthesis of Functionalized 1,3-Bis-Exocyclic Dienes via a Palladium-Catalyzed Reaction. Scope and Synthetic Applications

Thierry Lomberget, Didier Bouyssi, Geneviève Balme*
Laboratoire de Chimie Organique 1, associé au CNRS, Université Claude Bernard Lyon 1, CPE, 43 Bd du 11 Novembre 1918, 69622 Villeurbanne, France
Fax: +33(4)72431214; e-Mail: balme@univ-lyon1.fr;
Further Information

Publication History

Received 26 April 2004
Publication Date:
21 October 2004 (online)

    Permissions and Reprints All articles of this category

Abstract

The palladium-catalyzed tandem cyclization-coupling reaction of conjugated enynes having a stabilizing carbon nucleophile with aryl iodides and vinyl halides or triflates produced stereo­defined, functionalized five- and six-membered 1,3-bis-exocyclic dienes in moderate to good yields. These stereodefined dienes proved to be versatile substrates for the preparation of various polycyclic products through subsequent Diels-Alder, intramolecular Friedel-Crafts or thermal electrocyclization reactions.

  • 1 Introduction

  • 2 Formation of Cyclopentanic Derivatives

  • 3 Formation of Cyclohexanic Derivatives

  • 3.1 Synthesis of 1,3-Bis-Exocyclic Dienes

  • 3.2 Synthesis of Conjugated Trienes

  • 4 Synthetic Applications

  • 4.1 Diels-Alder Reaction

  • 4.2 Intramolecular Friedel-Crafts Reaction

  • 4.3 Thermal Electrocyclization

  • 4.3.1 Reaction on Conjugated Exocyclic Trienes

  • 4.3.2 One-Pot Synthesis of Functionalized Cyclohexadienes

  • 5 Conclusion

Key words

palladium - cyclization - enynes - exocyclic dienes - electrocyclization

    References

  • 1a Handbook of Organopalladium Chemistry for Organic Synthesis   Vol. 1 and 2:  Negishi E.-I. John Wiley and Sons; New York: 2002. 
  • 1b Poli G. Giambastiani G. Heumann A. Tetrahedron  2000,  56:  5959 
    Search in Google Scholar
  • 1c de Meijere A. Bräse S. J. Organomet. Chem.  1999,  576:  88 
    Search in Google Scholar
  • 1d Bräse S. de Meijere A. In Metal-catalyzed Cross-coupling Reactions   Diederich F. Stang PJ. Wiley-VCH; Weinheim: 1998.  p.99 
  • 1e Tetrahedron Symposium-in-Print  1996,  52:  Vol. 35 
  • 1f Tsuji J. Palladium Reagents and Catalysts: Innovations in Organic Synthesis   Wiley & Sons; Chichester: 1995. 
  • 1g Bunce RA. Tetrahedron  1995,  51:  13103 
    Search in Google Scholar
  • 1h Tietze LF. Beifuss U. Angew. Chem., Int. Ed. Engl.  1993,  32:  131 
    Search in Google Scholar
  • 1i Ho TL. Tandem Organic Reactions   Wiley Interscience; New York: 1992. 
  • 1j Overman LE. Abelman MM. Kucera DJ. Tran VD. Ricca DJ. Pure Appl. Chem.  1992,  64:  1813 
    Search in Google Scholar
  • 1k Negishi E.-I. Pure Appl. Chem.  1992,  64:  323 
    Search in Google Scholar
  • 2a Balme G. Bouyssi D. Lomberget T. Monteiro N. Synthesis  2003,  2115 
    Thieme Connect
  • 2b For reactions involving carbonucleophiles, see: Balme G. Bouyssi D. Monteiro N. In Handbook of Organopalladium Chemistry for Organic Synthesis   Negishi E.-i. Wiley Interscience; New York: 2002.  p.2245 
    Thieme Connect
  • 2c For oxygen nucleophile, see: Cacchi S. Arcadi A. In Handbook of Organopalladium Chemistry for Organic Synthesis   Negishi E.-i. Wiley Interscience; New York: 2002.  p.2193-2210  
    Thieme Connect
  • 2d For nitrogen nucleophiles, see: Cacchi S. Marinelli F. In Handbook of Organopalladium Chemistry for Organic Synthesis   Negishi E.-i. Wiley Interscience; New York: 2002.  p.2227-2244  
    Thieme Connect
  • 3a Balme G. Bouyssi D. Tetrahedron  1994,  50:  403 
    CrossrefPubMedSearch in Google Scholar
  • 3b Coudanne I. Balme G. Synlett  1998,  998 
    CrossrefPubMed
  • 3c Bruyère D. Gaignard G. Bouyssi D. Balme G. Lancelin JM. Tetrahedron Lett.  1997,  38:  827 
    CrossrefPubMedSearch in Google Scholar
  • 3d Garçon S. Vassiliou S. Cavicchioli M. Hartmann B. Monteiro N. Balme G. J. Org. Chem.  2001,  66:  4069 , and references cited therein
    CrossrefPubMedSearch in Google Scholar
  • For some examples using organometallic compounds, see:
  • 4a Nugent WA. Thorn DL. Harlow RL. J. Am. Chem. Soc.  1987,  109:  2788 
    CrossrefSearch in Google Scholar
  • 4b Bailey WF. Wachter-Jurcsak NM. Pineau MR. Ovaska TV. Warren RR. Lewis CE. J. Org. Chem.  1996,  61:  8216 
    CrossrefSearch in Google Scholar
  • 4c Urabe H. Nakajima R. Sato F. Org. Lett.  2000,  2:  3481 
    CrossrefSearch in Google Scholar
  • 4d Trost BM. Hipskind PA. Chung JYL. Chan C. Angew. Chem., Int. Ed. Engl.  1989,  28:  1502 
    CrossrefSearch in Google Scholar
  • 4e Meyer FE. Ang KH. Steinig AG. de Meijere A. Synlett  1994,  191 
    Crossref
  • 4f Wang X. Chakrapani H. Madine JW. Keyerleber MA. Widenhoefer RA. J. Org. Chem.  2002,  67:  2778 
    CrossrefSearch in Google Scholar
  • 4g Mori M. Kozawa Y. Nishida M. Kanamaru M. Onozuka K. Takimoto M. Org. Lett.  2000,  2:  3245 
    CrossrefSearch in Google Scholar
  • 4h Trost BM. Pfrengle W. Urabe H. Dumas J. J. Am. Chem. Soc.  1992,  114:  1923 
    CrossrefSearch in Google Scholar
  • 4i Grigg R. Savic V. Tetrahedron Lett.  1996,  37:  6565 
    CrossrefSearch in Google Scholar
  • 4j Meyer FE. Henniges H. de Meijere A. Tetrahedron Lett.  1992,  33:  8039 
    CrossrefSearch in Google Scholar
  • 4k Trost BM. Shi Y. J. Am. Chem. Soc.  1993,  115:  12491 
    CrossrefSearch in Google Scholar
  • 5 For the preliminary communication concerning this work, see: Lomberget T. Bouyssi D. Balme G. Synlett  2002,  1439 
    Thieme Connect
  • 6a Cousseau J. Synthesis  1980,  805 
    Crossref
  • 6b Barton TJ. Lin J. Ijadi-Maghsoodi S. Power MD. Zhang X. Ma Z. Shimizu H. Gordon MS. J. Am. Chem. Soc.  1995,  117:  11695 
    CrossrefSearch in Google Scholar
  • The palladium(0) catalyst generated in situ by reduction of PdCl2 (PPh3)2 with n-BuLi has been found particularly effective in related carbopalladation reactions:
  • 8a

    See ref. 3d.
    Crossref
  • 8b Bottex M. Cavicchioli M. Hartmann B. Monteiro N. Balme G. J. Org. Chem.  2001,  66:  175 
    CrossrefSearch in Google Scholar
  • 9 For mechanistic insights concerning the palladium(0) catalyst generated in situ by reduction of PdCl2 (PPh3)2 with n-BuLi, see: Amatore C. Azzabi M. Jutand A. J. Am. Chem. Soc.  1991,  113:  1670 
    CrossrefSearch in Google Scholar
  • The demethoxycarbonylation of malonate ester using Krapcho’s conditions generally needs prolonged heating in polar solvent:
  • 10a Krapcho AP. Synthesis  1982,  805 
    Thieme Connect
  • 10b Krapcho AP. Synthesis  1982,  893 , the strain generated by the two contiguous exocyclic double bonds and the malonate could explain these rather mild conditions
    Thieme Connect
  • 11 The difference in the rate of cyclization between a malononitrile and dimethylmalonate or methylcyanoacetate derivative was already observed. See: Bouyssi D. Coudanne I. Uriot H. Gore J. Balme G. Tetrahedron Lett.  1995,  36:  8019 
    CrossrefSearch in Google Scholar
  • 12 Bouyssi D. Balme G. Fournet G. Monteiro N. Goré J. Tetrahedron Lett.  1991,  32:  1641 
    CrossrefSearch in Google Scholar
  • 13a Fournet G. Balme G. van Hemelryck B. Goré J. Tetrahedron Lett.  1990,  31:  5147 
    CrossrefSearch in Google Scholar
  • 13b Fournet G. Balme G. Goré J. Tetrahedron  1991,  47:  6293 
    CrossrefSearch in Google Scholar
  • 13c Coudanne I. PhD Thesis   Université Claude Bernard; Lyon: 1997. 
    Crossref
  • 14 Klusener PAA. Kulik W. Brandsma L. J. Org. Chem.  1987,  52:  5261 
    CrossrefSearch in Google Scholar
  • 16 Gregory K. Bremer M. von Ragué Schleyer P. Klusener PAA. Brandsma L. Angew. Chem., Int. Ed. Engl.  1989,  28:  1224 
    CrossrefSearch in Google Scholar
  • 17 Koradin C. Rodriguez A. Knochel P. Synlett  2000,  1452 
    Thieme Connect
  • 18 For an other example of a copper-free Sonogashira coupling see: Böhm VPW. Hermann WA. Eur. J. Org. Chem.  2000,  3679 
    Crossref
  • The synthetic utility of these dienic substrates 7e and 7f having an allylic sulfone would be of prime interest since they may allow further functionalization by allylic substitution. See:
  • 19a Simpkins NS. Sulphones in Organic Synthesis   Pergamon; Oxford: 1993. 
    Crossref
  • 19b Trost B. Bull. Chem. Soc. Jpn.  1988,  61:  107 
    CrossrefSearch in Google Scholar
  • 19c Woods M. Monteiro N. Balme G. Eur. J. Org. Chem.  2000,  1711 
    Crossref
  • 19d Clique B. Vassiliou S. Monteiro N. Balme G. Eur. J. Org. Chem.  2002,  1493 
    Crossref
  • For related examples of palladium-catalyzed reaction combined with 6-π electrocyclization processes, see:
  • 20a

    See ref. 4h-k.
  • 20b Gilchrist TL. Summersell RJ. Tetrahedron Lett.  1987,  28:  1469 
    Search in Google Scholar
  • 20c Gilchrist TL. Healy MAM. J. Chem. Soc., Perkin Trans. 1  1992,  749 
  • 20d von Zezschwitz P. Petry F. de Meijere A. Chem.-Eur. J.  2001,  7:  4035 
    Search in Google Scholar
  • Similar results were recently reported for palladium catalyzed tandem cyclization/coupling reactions involving commercial β-bromostyrene:
  • 21a

    See ref. 8b.
    Thieme Connect
  • 21b Arcadi A. Cacchi S. Cassetta A. Fabrizi G. Parisi LM. Synlett  2001,  1605 
    Thieme Connect
  • 22 Lomberget T. Chataigner I. Bouyssi D. Maddaluno J. Balme G. Tetrahedron Lett.  2004,  45:  3437 
    CrossrefSearch in Google Scholar
  • 23 Lomberget T. Bentz E. Bouyssi D. Balme G. Org. Lett.  2003,  5:  2055 
    CrossrefSearch in Google Scholar
  • 24a Lin W.-H. Fang J.-M. Cheng Y.-S. Phytochemistry  1995,  40:  871 
    CrossrefSearch in Google Scholar
  • 24b Ohtsu H. Iwamoto M. Ohishi H. Matsunaga S. Tanaka R. Tetrahedron Lett.  1999,  40:  6419 
    CrossrefSearch in Google Scholar
  • 24c Kawazoe K. Yamamoto M. Takaishi Y. Honda G. Fujita T. Sezik E. Yesilada E. Phytochemistry  1999,  50:  493 
    CrossrefSearch in Google Scholar
  • 25 Marvell EN. Thermal Electrocyclic Reactions   Academic Press; New York: 1980. 
  • 26 Burchat AF. Chong JM. Nielsen N. J. Organomet. Chem.  1997,  542:  281 
    CrossrefSearch in Google Scholar
  • 27 Coulson DR. Inorg. Synth.  1974,  13:  121 
    Search in Google Scholar
7

The palladium(0)-diphenylphosphinoethane was preformed by heating Pd(OAc)2 (5 mol%) and dppe (5 mol%) in the presence of 1-heptene (10 mol%, THF 50 °C) until a homogeneous dark red solution was obtained.

15

The stereochemistry of the substituted double bond is defined by the mechanism of the Wacker-type reaction. [2] The E configuration of 7a was confirmed by a NOESY experiment in the 1H NMR.