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Synthesis 2009(13): 2260-2266  
DOI: 10.1055/s-0029-1216819
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

o-Benzenedisulfonimide as a Powerful and Recyclable Organocatalyst for the Nazarov Reaction

Margherita Barbero*a, Silvano Cadamuroa, Annamaria Deagostinoa, Stefano Dugheraa, Paolo Larinia, Ernesto G. Occhiatob, Cristina Prandi*a, Silvia Tabassoa, Rosaria Vulcanoa, Paolo Venturelloa
a Dipartimento di Chimica Generale e Chimica Organica, Università, Via P. Giuria 7, 10125 Torino, Italy
Fax: +39(011)7642; e-Mail: cristina.prandi@unito.it; e-Mail: margherita.barbero@unito.it;
b Dipartimento di Chimica Organica ‘U. Schiff’, and HeteroBioLab, Università di Firenze, Via della Lastruccia 13, 50019 Sesto Fiorentino, Italy
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Publikationsverlauf

Received 13 February 2009
Publikationsdatum:
14. Mai 2009 (online)

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Abstract

o-Benzenedisulfonimide has been used for the first time as a Brønsted acid catalyst to induce electrocyclization of dienones into cyclopentenones (Nazarov reaction). The catalyst has been used in various organic solvents or under solvent-free conditions and it is entirely recoverable from the reaction mixture. The versatility and the effectiveness of the proposed procedure is demonstrated on a wide range of both activated and inactivated substrates.

Key words

Nazarov reaction - Brønsted acid - cyclization - organocatalysis - cyclopentenones

    References

  • For reviews see:
  • 1a Frontier AJ. Collison C. Tetrahedron  2005,  61:  7577 
    Suche in Google Scholar
  • 1b Pellissier H. Tetrahedron  2005,  61:  6479 
    Suche in Google Scholar
  • 1c Tius MA. Eur. J. Org. Chem.  2005,  2193 
  • 1d Habermas KL. Denmark SE. Jones TK. Org. React.  1994,  45:  1 
    Suche in Google Scholar
  • 2 Douelle F. Tal L. Greaney MF. Chem. Commun.  2005,  660 
    Crossref
  • For selected Lewis acid promoted Nazarov cyclizations, see:
  • 3a Zhu J. Zhong C. Lu HF. Li GY. Sun X. Synlett  2008,  458 
  • 3b He W. Huang J. Sun XF. Frontier AJ. J. Am. Chem. Soc.  2008,  130:  300 
    Suche in Google Scholar
  • 3c He W. Herrick R. Atesin TA. Caruana PA. Kellenberger CA. Frontier AJ. J. Am. Chem. Soc.  2008,  130:  1003 
    Suche in Google Scholar
  • 3d Song D. Rostami A. West FG. J. Am. Chem. Soc.  2007,  129:  12019 
    Suche in Google Scholar
  • 3e Cui HF. Dong KY. Zhang GW. Wang L. Ma JA. Chem. Commun.  2007,  2284 
  • 3f Shindo M. Yaji K. Kita T. Shishido KK. Synlett  2007,  1096 
  • 3g Bartali L. Larini P. Guarna A. Occhiato EG. Synthesis  2007,  1733 
  • 3h Larini P. Guarna A. Occhiato EG. Org. Lett.  2006,  8:  781 
    Suche in Google Scholar
  • 3i Bartali L. Guarna A. Larini P. Occhiato EG. Eur. J. Org. Chem.  2007,  2152 
  • 3j White TD. West FG. Tetrahedron Lett.  2005,  46:  5629 
    Suche in Google Scholar
  • 3k Giese S. West FG. Tetrahedron  2000,  56:  10221 
    Suche in Google Scholar
  • 3l Aggarwal VK. Beffield AJ. Org. Lett.  2003,  5:  5075 ; and references cited therein
    Suche in Google Scholar
  • 3m Irgolic KJ. In Houben-Weyl   4th ed., Vol. E12b:  Klamann D. Georg Thieme Verlag; Stuttgart: 1990.  p.150 
    Suche in Google Scholar
  • 4 Leikoski T. Kaunisto J. Alkio M. Aaltonen Yli-Kauhaluoma OJ. Org. Process Res. Dev.  2005,  9:  629 ; see ref. 6 for references on Nazarov reactions catalyzed by mineral Brønsted acids
    CrossrefSuche in Google Scholar
  • 5a Ishikura M. Imaizumi K. Katagiri N. Heterocycles  2000,  53:  2201 
    Suche in Google Scholar
  • 5b Barluenga J. Barrio P. Vicente R. Lopez LA. Tomas M. J. Organomet. Chem.  2004,  689:  3793 
    Suche in Google Scholar
  • 6 Amere M. Blanchet J. Lasne MC. Rouden J. Tetrahedron Lett.  2008,  49:  2541 
    CrossrefSuche in Google Scholar
  • 7a Prandi C. Ferrali A. Guarna A. Venturello P. Occhiato EG. J. Org. Chem.  2004,  69:  7705 
    Suche in Google Scholar
  • 7b Occhiato EG. Prandi C. Ferrali A. Guarna A. Venturello P. J. Org. Chem.  2003,  68:  9728 
    Suche in Google Scholar
  • 7c Occhiato EG. Prandi C. Ferrali A. Guarna A. Deagostino A. Venturello P. J. Org. Chem.  2002,  67:  7144 ; and references therein
    Suche in Google Scholar
  • 8 Basak AK. Tius MA. Org. Lett.  2008,  10:  4073 
    CrossrefSuche in Google Scholar
  • 9a Nie J. Zhu HW. Cui HF. Hua MQ. Ma JA. Org. Lett.  2007,  9:  3053 
    Suche in Google Scholar
  • 9b Tius MA. Acc. Chem. Res.  2003,  36:  284 
    Suche in Google Scholar
  • 9c Liang GX. Gradl SN. Trauner D. Org. Lett.  2003,  5:  4931 
    Suche in Google Scholar
  • 9d Kerr DJ. Metje C. Flynn CL. Chem. Commun.  2003,  1380 
  • 9e Pridgen LN. Huang K. Shilcrat S. Tickner-Eldridge A. DeBrosse C. Haltiwanger RC. Synlett  1999,  1612 
  • 9f Bond CS. Leonard GA. Regan AC. Hunter V. Andrews JFP. Acta Crystallogr., Sect. C  1994,  50:  133 
    Suche in Google Scholar
  • 10 Rueping M. Ieawsuwan W. Antonchick AP. Nachtsheim BJ. Angew. Chem. Int. Ed.  2007,  46:  2097 
    CrossrefSuche in Google Scholar
  • 11a Barbero M. Cadamuro S. Dughera S. Venturello P. Synlett  2007,  2209 
  • 11b Barbero M. Cadamuro S. Sughera S. Venturello P. Synthesis  2008,  1379 
  • 11c Barbero M. Cadamuro S. Dughera S. Venturello P. Synthesis  2008,  3625 
  • 11d Barbero M. Cadamuro S. Dughera S. Eur. J. Org. Chem.  2009,  430 
  • 12a Cavalli A. Pacetti A. Recanatini M. Prandi C. Scarpi D. Occhiato EG. Chem. Eur. J.  2008,  14:  9292 
    Suche in Google Scholar
  • 12b Cavalli A. Masetti M. Recanatini M. Prandi C. Guarna A. Occhiato EG. Chem. Eur. J.  2006,  12:  2836 
    Suche in Google Scholar
  • 12c Prandi C. Deagostino A. Venturello P. Occhiato EG. Org. Lett.  2005,  7:  4345 
    Suche in Google Scholar
  • 12d Occhiato EG. Prandi C. Ferrali A. Guarna A. J. Org. Chem.  2005,  70:  4542 
    Suche in Google Scholar
  • 12e Deagostino A. Migliardi M. Occhiato EG. Prandi C. Zavattaro C. Venturello P. Tetrahedron  2005,  61:  3429 
    Suche in Google Scholar
  • 13 von Ohloff G. Schulte-Elte KH. Demole E. Helv. Chim. Acta  1971,  54:  2913 
    CrossrefSuche in Google Scholar
  • 16 Deagostino A. Larini P. Occhiato EG. Pizzuto L. Prandi C. Venturello P. J. Org. Chem.  2008,  73:  1941 
    CrossrefSuche in Google Scholar
  • 20 Bee C. Leclerc E. Tius MA. Org. Lett.  2003,  5:  4927 ; under these experimental conditions, 4 was isolated starting from 2i (see experimental section). Further studies are ongoing in our laboratory aimed at optimizing the experimental conditions and at expanding the scope of the reaction
    CrossrefSuche in Google Scholar
14

Unpublished results from these laboratories.

15

In experiments conducted on a 10-mmol scale, according to the conditions indicated in Table 1, entry 11, the catalyst has been recovered as already reported¹¹d from the reaction mixture and recycled up to three times without a significant loss of catalytic activity.

17

During the progress of the reaction, the TLC control revealed the conversion of the allyl derivatives 2b and 2d into an intermediate that precedes the formation of the final product.

18

For an exhaustive discussion of the pattern of substitution of dienone on reactivity in Nazarov cyclization see ref. 3c and references therein. For effects of electron donor β-substi­-tuents see ref. 3f. For DFT calculations on reactivity of heterocyclic derivatives in Nazarov cyclization see ref. 12a and 12b.

19

Compounds 2h-j have been unsuccessfully subjected to Nazarov cyclization under the following conditions: Amberlyst in CH2Cl2, Amberlyst in toluene at 60 ˚C, 5% Cu(OTf)2 in CH2Cl2 at r.t.