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
Further Information

Publication History

Received 13 February 2009
Publication Date:
14 May 2009 (eFirst)

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.

    References

  • For reviews see:
  • 1a Frontier AJ. Collison C. Tetrahedron  2005,  61:  7577 
  • 1b Pellissier H. Tetrahedron  2005,  61:  6479 
  • 1c Tius MA. Eur. J. Org. Chem.  2005,  2193 
  • 1d Habermas KL. Denmark SE. Jones TK. Org. React.  1994,  45:  1 
  • 2 Douelle F. Tal L. Greaney MF. Chem. Commun.  2005,  660 
  • 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 
  • 3c He W. Herrick R. Atesin TA. Caruana PA. Kellenberger CA. Frontier AJ. J. Am. Chem. Soc.  2008,  130:  1003 
  • 3d Song D. Rostami A. West FG. J. Am. Chem. Soc.  2007,  129:  12019 
  • 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 
  • 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 
  • 3k Giese S. West FG. Tetrahedron  2000,  56:  10221 
  • 3l Aggarwal VK. Beffield AJ. Org. Lett.  2003,  5:  5075 ; and references cited therein
  • 3m Irgolic KJ. In Houben-Weyl   4th ed., Vol. E12b:  Klamann D. Georg Thieme Verlag; Stuttgart: 1990.  p.150 
  • 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
  • 5a Ishikura M. Imaizumi K. Katagiri N. Heterocycles  2000,  53:  2201 
  • 5b Barluenga J. Barrio P. Vicente R. Lopez LA. Tomas M. J. Organomet. Chem.  2004,  689:  3793 
  • 6 Amere M. Blanchet J. Lasne MC. Rouden J. Tetrahedron Lett.  2008,  49:  2541 
  • 7a Prandi C. Ferrali A. Guarna A. Venturello P. Occhiato EG. J. Org. Chem.  2004,  69:  7705 
  • 7b Occhiato EG. Prandi C. Ferrali A. Guarna A. Venturello P. J. Org. Chem.  2003,  68:  9728 
  • 7c Occhiato EG. Prandi C. Ferrali A. Guarna A. Deagostino A. Venturello P. J. Org. Chem.  2002,  67:  7144 ; and references therein
  • 8 Basak AK. Tius MA. Org. Lett.  2008,  10:  4073 
  • 9a Nie J. Zhu HW. Cui HF. Hua MQ. Ma JA. Org. Lett.  2007,  9:  3053 
  • 9b Tius MA. Acc. Chem. Res.  2003,  36:  284 
  • 9c Liang GX. Gradl SN. Trauner D. Org. Lett.  2003,  5:  4931 
  • 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 
  • 10 Rueping M. Ieawsuwan W. Antonchick AP. Nachtsheim BJ. Angew. Chem. Int. Ed.  2007,  46:  2097 
  • 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 
  • 12b Cavalli A. Masetti M. Recanatini M. Prandi C. Guarna A. Occhiato EG. Chem. Eur. J.  2006,  12:  2836 
  • 12c Prandi C. Deagostino A. Venturello P. Occhiato EG. Org. Lett.  2005,  7:  4345 
  • 12d Occhiato EG. Prandi C. Ferrali A. Guarna A. J. Org. Chem.  2005,  70:  4542 
  • 12e Deagostino A. Migliardi M. Occhiato EG. Prandi C. Zavattaro C. Venturello P. Tetrahedron  2005,  61:  3429 
  • 13 von Ohloff G. Schulte-Elte KH. Demole E. Helv. Chim. Acta  1971,  54:  2913 
  • 16 Deagostino A. Larini P. Occhiato EG. Pizzuto L. Prandi C. Venturello P. J. Org. Chem.  2008,  73:  1941 
  • 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
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.