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Synthesis 2010(4): 701-713  
DOI: 10.1055/s-0029-1218645
FEATUREARTICLE
© Georg Thieme Verlag Stuttgart ˙ New York

‘On Water’ Iminium/Enamine Catalysis: Organocatalytic Enantioselective Cyclopropanation of α,β-Unsaturated Aldehydes

Uxue Uria, Jose L. Vicario*, Dolores Badía, Luisa Carrillo, Efraim Reyes, Amaia Pesquera
Departamento de Química Orgánica II, Facultad de Ciencia y Tecnología, Universidad del País Vasco/Euskal Herriko Unibertsitatea, P.O. Box 644, 48080 Bilbao, Spain
Fax: +34(94)6012748; e-Mail: joseluis.vicario@ehu.es;
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Publication History

Received 11 November 2009
Publication Date:
12 January 2010 (online)

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Abstract

We have developed a very efficient procedure for carrying out the cyclopropanation reaction of α,β-unsaturated aldehydes with diethyl bromomalonate using an O-TMS-diarylprolinol as a catalyst. We have found that the use of water as reaction medium results in a remarkable beneficial effect on the reaction, allowing it to be performed without the need to incorporate one equivalent of an external base, which is the case in other similar methodologies reported. In addition, several new chiral pyrrolidines have been prepared that have potential for improved ability as a catalyst for this transformation in aqueous media. In this context, a modified O-TMS-diarylprolinol incorporating a hydrophobic alkyl side chain has been identified as a promising catalyst for this reaction.

Key words

asymmetric catalysis - domino reaction - Michael addition - organocatalysis - ‘on water’ reaction

    References

  • For some selected general reviews on asymmetric organocatalysis, see:
  • 1a Melchiorre P. Marigo M. Carlone A. Bartoli G. Angew. Chem. Int. Ed.  2008,  47:  6138 
    Google Scholar
  • 1b Dondoni A. Massi A. Angew. Chem. Int. Ed.  2008,  47:  4638 
    Google Scholar
  • 1c Special issue on organocatalysis: Chem. Rev.  2007,  107:  5413-5883  
    Google Scholar
  • 1d List B. Yang J.-W. Science  2006,  313:  1584 
    Google Scholar
  • 1e MacMillan DWC. Nature  2008,  455:  304 
    Google Scholar
  • 2 List B. Lerner RA. Barbas CF. J. Am. Chem. Soc.  2000,  122:  2395 
    CrossrefGoogle Scholar
  • 3 Ahrendt KA. Borths CJ. MacMillan DWC. J. Am. Chem. Soc.  2000,  122:  4243 
    CrossrefGoogle Scholar
  • For some reviews see:
  • 4a Vicario JL. Badia D. Carrillo L. Synthesis  2007,  2065 
    Google Scholar
  • 4b Almaçi D. Alonso DA. Nájera C. Tetrahedron: Asymmetry  2007,  18:  299 
    Google Scholar
  • 4c Tsogoeva SB. Eur. J. Org. Chem.  2007,  1701 
    Google Scholar
  • 4d Sulzer-Mosse S. Alexakis A. Chem. Commun.  2007,  3123 
    Google Scholar
  • 5a Yu X. Wang W. Org. Biomol. Chem.  2008,  6:  2037 
    Google Scholar
  • 5b Enders D. Grondal C. Huettl MRM. Angew. Chem. Int. Ed.  2007,  46:  1570 
    Google Scholar
  • 5c Guillena G. Ramon DJ. Yus M. Tetrahedron: Asymmetry  2007,  18:  693 
    Google Scholar
  • 6 Reyes E. Vicario JL. Badia D. Carrillo L. Org. Lett.  2006,  8:  6135 
    CrossrefGoogle Scholar
  • 7 Ruiz N. Reyes E. Vicario JL. Badia D. Carrillo L. Uria U. Chem. Eur. J.  2008,  14:  9357 
    CrossrefGoogle Scholar
  • 8 Uria U. Vicario JL. Badia D. Carrillo L. Chem. Commun.  2007,  2509 
    CrossrefGoogle Scholar
  • 9 Reyes E. Talavera G. Vicario JL. Badia D. Carrillo L. Angew. Chem. Int. Ed.  2009,  48:  5701 
    CrossrefGoogle Scholar
  • For some reviews, see:
  • 10a Gruttadauria M. Giacalone F. Noto R. Adv. Synth. Catal.  2009,  351:  33 
    Google Scholar
  • 10b Brogan AP. Dickerson TJ. Janda KD. Angew. Chem. Int. Ed.  2006,  45:  8100 
    Google Scholar
  • See also
  • 10c Blackmond DG. Armstrong A. Coombe V. Wells A. Angew. Chem. Int. Ed.  2007,  46:  3798 
    Google Scholar
  • 10d Jung Y. Marcus RA. J. Am. Chem. Soc.  2007,  129:  5492 
    Google Scholar
  • 11 Narayan S. Muldoon J. Finn MG. Fokin VV. Kolb HC. Sharpless KB. Angew. Chem. Int. Ed.  2005,  44:  3275 
    CrossrefPubMedGoogle Scholar
  • 12 For a recent general review, see: Chanda A. Fokin VV. Chem. Rev.  2009,  109:  725 
    CrossrefPubMedGoogle Scholar
  • 13a Wong HNC. Hon M.-Y. Tse C.-W. Yip Y.-C. Tanko J. Hudlicky T. Chem Rev.  1989,  89:  165 
    Google Scholar
  • 13b

    See also refs. 14 and 15 and references therein.

  • 14a Special issue on cyclopropanes and related rings: Chem. Rev.  2003,  103:  931-1648  
    Google Scholar
  • 14b

    See also ref. 15 and references therein.

  • 15 Sitachitta N. Gerwick W. J. Nat. Prod.  1998,  61:  681 
    CrossrefPubMedGoogle Scholar
  • 16 Martoin E. Quinke K. Spahn H. Mutschler E. Chirality  1989,  1:  223 
    CrossrefGoogle Scholar
  • 17 For a review: Barlow SM. Sullivan FM. Lines J. Food Chem. Toxicol.  2001,  39:  407 
    CrossrefGoogle Scholar
  • 18a Davoren JE. Martin SF. J. Am. Chem. Soc.  2007,  129:  510 
    Google Scholar
  • 18b Pietruszka J. Rieche ACM. Adv. Synth. Catal.  2008,  350:  1407 
    Google Scholar
  • 18c White JD. Lincoln CM. Yang J. Martin WHC. Chan DB. J. Org. Chem.  2008,  73:  4139 
    Google Scholar
  • 19 For a recent review on asymmetric cyclopropanations, see: Pellissier H. Tetrahedron  2008,  64:  7041 
    Google Scholar
  • For some examples of organocatalytic asymmetric syntheses of cyclopropanes see:
  • 20a Kunz RK. MacMillan DWC. J. Am. Chem. Soc.  2005,  127:  3240 
    Google Scholar
  • 20b Hartikka A. Œlósarczyk AT. Arvidsson PI. Tetrahedron: Asymmetry  2007,  18:  1403 
    Google Scholar
  • 20c Hartikka A. Arvidsson PI. J. Org. Chem.  2007,  72:  5874 
    Google Scholar
  • 20d Zhao Y.-H. Zhao G. Cao WG. Tetrahedron: Asymmetry  2007,  18:  2462 
    Google Scholar
  • 20e Zhao Y.-H. Zheng C.-W. Zhao G. Cao W.-G. Tetrahedron: Asymmetry  2008,  19:  701 
    Google Scholar
  • 20f Papageorgiou CD. Cubillo de Dios MA. Ley SV. Gaunt MJ. Angew. Chem. Int. Ed.  2004,  43:  4641 
    Google Scholar
  • 20g Johansson CCC. Bremeyer N. Ley SV. Owen DR. Smith SC. Gaunt MJ. Angew. Chem. Int. Ed.  2006,  45:  6024 
    Google Scholar
  • 20h Deng X.-M. Cai P. Ye S. Sun X.-L. Liao W.-W. Li K. Tang Y. Wu Y.-D. Dai L.-X. J. Am. Chem. Soc.  2006,  128:  9730 
    Google Scholar
  • 20i Liao W.-W. Li K. Tang Y. J. Am. Chem. Soc.  2003,  125:  13030 
    Google Scholar
  • 20j Kojima S. Suzuki M. Watanabe A. Ohkata K. Tetrahedron Lett.  2006,  47:  9061 
    Google Scholar
  • 20k Xuan Y.-N. Nie S.-Z. Dong L.-T. Zhang J.-M. Yan M. Org. Lett.  2009,  11:  1583 
    Google Scholar
  • 20l McCooey SH. McCabe T. Connon SJ. J. Org. Chem.  2006,  71:  7494 
    Google Scholar
  • 20m Inokuma T. Sakamoto S. Takemoto Y. Synlett  2009,  1627 
    Google Scholar
  • 20n Arai S. Nakayama K. Ishida T. Shioiri T. Tetrahedron Lett.  1999,  40:  4215 
    Google Scholar
  • 21a Hansen HM. Longbottom DA. Ley SV. Chem. Commun.  2006,  4838 
    Google Scholar
  • See also:
  • 21b Wascholowski V. Hansen HM. Longbottom DA. Ley SV. Synthesis  2008,  1269 
    Google Scholar
  • For related examples, see:
  • 21c Lv J. Zhang J. Lin Z. Wang Y. Chem. Eur. J.  2009,  15:  972 
    Google Scholar
  • 21d Vesely J. Zhao G.-L. Bartoszewicz A. Córdova A. Tetrahedron Lett.  2008,  49:  4209 
    Google Scholar
  • 21e

    See also refs. 22 and 23.

    Google Scholar
  • 22a Companyó X. Alba A.-N. Cárdenas F. Moyano A. Rios R. Eur. J. Org. Chem.  2009,  3075 
    Google Scholar
  • 22b Ibrahem I. Zhao G.-L. Rios R. Vesely J. Sundén H. Dziedzic P. Córdova A. Chem. Eur. J.  2008,  14:  7867 
    Google Scholar
  • 22c Rios R. Sundén H. Vesely J. Zhao G.-L. Dziedzic P. Córdova A. Adv. Synth. Catal.  2007,  349:  1028 
    Google Scholar
  • 22d Xie H. Zu L. Li H. Wang J. Wang W. J. Am. Chem. Soc.  2007,  129:  10886 
    Google Scholar
  • 23 For a selected example of acceleration of an organocatalytic Michael reaction via enamine catalysis ‘on water’ using catalyst 4b see: Zhu S. Yu S. Ma D. Angew. Chem. Int. Ed.  2008,  47:  545 
    CrossrefGoogle Scholar
  • For some reviews on the use of diarylprolinols as catalysts see:
  • 24a Palomo C. Mielgo A. Angew. Chem. Int. Ed.  2006,  45:  7876 
    Google Scholar
  • 24b Mielgo A. Palomo C. Chem. Asian J.  2008,  3:  922 
    Google Scholar
  • 25a Franzén J. Marigo M. Fielenbach D. Wabnitz TC. Kjaersgaard A. Jørgensen KA. J. Am. Chem. Soc.  2005,  127:  18296 
    Google Scholar
  • See also:
  • 25b Hayashi Y. Gotoh H. Hayasi T. Shoji M. Angew. Chem. Int. Ed.  2005,  44:  4212 
    Google Scholar
  • See, for example:
  • 26a Alza E. Cambeiro XC. Jimeno C. Pericàs MA. Org. Lett.  2007,  9:  3717 
    Google Scholar
  • 26b Palomo C. Landa A. Mielgo A. Oiarbide M. Puente A. Vera S. Angew. Chem. Int. Ed.  2007,  46:  8431 
    Google Scholar
  • 26c Mase N. Nakai Y. Ohara N. Yoda H. Takabe K. Tanaka F. Barbas CF. J. Am. Chem. Soc.  2006,  128:  734 
    Google Scholar
  • 26d Mase N. Watanabe K. Yoda H. Takabe K. Yanaka F. Barbas CF. J. Am. Chem. Soc.  2006,  128:  4966 
    Google Scholar
  • 26e Yang H. Carter RG. Org. Lett.  2008,  10:  4649 
    Google Scholar
  • 27 Pickering L. Malhi BS. Coe PL. Walker RT. Tetrahedron  1995,  51:  2719 
    CrossrefGoogle Scholar
  • 28 Itoh T. Ishikawa H. Hayashi Y. Org. Lett.  2009,  11:  3854 
    CrossrefPubMedGoogle Scholar