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Synlett 2009(10): 1675-1679  
DOI: 10.1055/s-0029-1217332
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© Georg Thieme Verlag Stuttgart ˙ New York

Reaction Rate Acceleration Enabled by Tethered Lewis Acid-Lewis Base Bifunctional Catalysis: A Catalytic, Enantioselective [2+2] Ketene Aldehyde Cycloaddition Reaction

Sridhar Chidara, Yun-Ming Lin*
Department of Chemistry, University of Toledo, 2801 W. Bancroft Street, Toledo, OH 43606, USA
Fax: +1(419)5304033; e-Mail: Yun-Ming.Lin@Utoledo.edu;
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Publication History

Received 2 March 2009
Publication Date:
02 June 2009 (online)

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Abstract

A tethered Lewis acid-Lewis base (LA*-LB*) bifunctional catalyst promotes the asymmetric [2+2] cycloaddition reaction between ketene and aldehydes rapidly. The LA*-LB* bifunctional catalyst, a quinine tethered Co(III)-salen complex (5 mol%) catalyzes the [2+2] cycloaddition reaction to produce the C4-substituted β-lactones in uniformly >99% ee and high isolated yields (71-97%). The dramatic rate acceleration, the hallmark of cooperative intramolecular bifunctional catalysis, is achieved for the catalytic, enantioselective [2+2] cycloaddition reaction between aldehydes and unsubstituted ketene.

Key words

Lewis acids - Lewis bases - bifunctional catalysts - rate acceleration - enantioselectivity

    References and Notes

  • For selected reviews on β-lactones and their synthetic applications, see:
  • 1a Pommier A. Pons J.-M. Synthesis  1993,  441 
    Google Scholar
  • 1b Yang HW. Romo D. Tetrahedron  1999,  55:  6403 
    Google Scholar
  • 1c Schneider C. Angew. Chem. Int. Ed.  2002,  41:  744 ; Angew. Chem. 2002, 114, 771
    Google Scholar
  • 1d Wang Y. Tennyson RL. Romo D. Heterocycles  2004,  64:  605 
    Google Scholar
  • For selected reviews, see:
  • 2a Tidwell TT. Eur. J. Org. Chem.  2006,  563 
    Google Scholar
  • 2b Orr RK. Calter MA. Tetrahedron  2003,  59:  3545 
    Google Scholar
  • For examples of β-lactone formation from silylketene, see:
  • 2c Evans DA. Janey JM. Org. Lett.  2001,  3:  2125 
    Google Scholar
  • 2d Forslund RE. Cain J. Colyer J. Doyle MP. Adv. Synth. Catal.  2005,  347:  87 
    Google Scholar
  • 3a Wynberg H. Staring EGJ. J. Am. Chem. Soc.  1982,  104:  166 
    Google Scholar
  • 3b Wynberg H. Staring EGJ. J. Org. Chem.  1985,  50:  1977 
    Google Scholar
  • 4 Cortez GS. Tennyson RL. Romo D. J. Am. Chem. Soc.  2001,  123:  7945 
    Google Scholar
  • 5a Nelson SG. Zhu C. Shen X. J. Am. Chem. Soc.  2004,  126:  14 
    Google Scholar
  • 5b Zhu C. Shen X. Nelson SG. J. Am. Chem. Soc.  2004,  126:  5352 
    Google Scholar
  • 5c Calter MA. Tretyak OA. Flascheriem C. Org. Lett.  2005,  7:  1809 
    Google Scholar
  • 6a Wilson JE. Fu GC. Angew. Chem. Int. Ed.  2004,  43:  6358 ; Angew. Chem. 2004, 116, 6518
    Google Scholar
  • 6b Gnanadesikan V. Corey EJ. Org. Lett.  2006,  8:  4943 
    Google Scholar
  • 6c Kull T. Peters R. Adv. Synth. Catal.  2007,  349:  1647 
    Google Scholar
  • 6d Kull T. Peters R. Angew. Chem. Int. Ed.  2008,  47:  5461 ; Angew. Chem. 2008, 120, 5541
    Google Scholar
  • 6e He L. Lv H. Zhang Y.-R. Ye S. J. Org. Chem.  2008,  73:  8101 
    Google Scholar
  • 7 Lin Y.-M. Boucau J. Li Z. Casarotto V. Lin J. Nguyen AN. Ehrmantraut J. Org. Lett.  2007,  9:  567 
    CrossrefGoogle Scholar
  • For selected reviews on tethered Lewis acid-Lewis base bifunctional catalysts, see:
  • 8a Paull DH. Abraham CJ. Scerba MT. Alden-Danforth E. Lectka T. Acc. Chem. Res.  2008,  41:  655 
    Google Scholar
  • 8b Kanai M. Kato N. Ichikawa E. Shibasaki M. Synlett  2005,  1491 
    Google Scholar
  • For selected examples of tethered bifunctional catalysts, see:
  • 8c Ito Y. Sawamura M. Hayashi T. J. Am. Chem. Soc.  1986,  108:  6405 
    Google Scholar
  • 8d Josephsohn NS. Kuntz KW. Snapper ML. Hoveyda AH. J. Am. Chem. Soc.  2001,  123:  11594 
    Google Scholar
  • 8e DiMauro EF. Kozlowski MC. Org. Lett.  2001,  3:  3053 
    Google Scholar
  • 8f Ichikawa E. Suzuki M. Yabu K. Albert M. Kanai M. Shibasaki M. J. Am. Chem. Soc.  2004,  126:  11808 
    Google Scholar
  • 8g France S. Shah MH. Weatherwax A. Wack H. Roth JP. Lectka T. J. Am. Chem. Soc.  2005,  127:  1206 
    Google Scholar
  • 8h Fennie MW. Dimauro EF. O’Brien EM. Annamalai V. Kozlowski MC. Tetrahedron  2005,  61:  6249 
    Google Scholar
  • 9 Lin Y.-M. Li Z. Boucau J. Tetrahedron Lett.  2007,  48:  5275 
    CrossrefGoogle Scholar
  • 11a Tokunaga M. Larrow JF. Kakiuchi F. Jacobsen EN. Science  1997,  277:  936 
    Google Scholar
  • 11b Jacobsen EN. Acc. Chem. Res.  2000,  33:  421 
    Google Scholar
  • 12 For an example of oxidizing a Co(II)-salen complex to the corresponding Co(III)-salen complex using AgSbF6, see: Hutson GE. Dave AH. Rawal VH. Org. Lett.  2007,  9:  3869 
    CrossrefGoogle Scholar
  • 13 Williams JW. Hurd CD. J. Org. Chem.  1940,  5:  122 
    CrossrefGoogle Scholar
  • For selected examples of catalytic asymmetric acetate aldol reactions, see:
  • 14a Mikami K. Matsukawa S. J. Am. Chem. Soc.  1994,  116:  4077 
    Google Scholar
  • 14b Carreira EM. Singer RA. Lee W. J. Am. Chem. Soc.  1994,  116:  8837 
    Google Scholar
  • 14c For an overview, see: Carreira EM. Fettes A. Marti C. In Organic Reactions   Vol. 67:  Overman LE. Wiley & Sons; New York: 2006.  p.1-216  ; and references cited therein
    Google Scholar
  • For selected reviews on organocatalysis, see:
  • 15a List B. Chem. Rev.  2007,  107:  5413 
    Google Scholar
  • 15b MacMillan DWC. Nature  2008,  455:  304 
    Google Scholar
  • 16 For a recent review on Lewis base catalysis, see: Denmark SE. Beutner GL. Angew. Chem. Int. Ed.  2008,  47:  1560 ; Angew. Chem. 2008, 120, 1584
    CrossrefPubMedGoogle Scholar
10

For examples of generating ketene from acyl halides and Hünig’s base in situ, see ref 2a and 5.