Download PDF
Synlett 2010(11): 1723-1728  
DOI: 10.1055/s-0029-1219963
CLUSTER
© Georg Thieme Verlag Stuttgart ˙ New York

Construction of Quaternary Stereogenic Carbon Centers by the Lewis Base Catalyzed Conjugate Addition of Silyl Ketene Imines to α,β-Unsaturated Aldehydes and Ketones

Scott E. Denmark*, Tyler W. Wilson
Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, IL 61801, USA
Fax: +1(217)3333984; e-Mail: sdenmark@illinois.edu;
Further Information

Publication History

Received 11 May 2010
Publication Date:
10 June 2010 (online)

    Permissions and Reprints All articles of this category

Abstract

Highly site-selective Mukaiyama-Michael additions of silyl ketene imines to α,β-unsaturated aldehydes and ketones are described. The combination of silicon tetrachloride and a chiral bisphosphoramide provides an effective catalyst system for promoting the addition of silyl ketene imines to a variety of aromatic enals with high site selectivity and moderate to good diastereo- and enantioselectivity.

Key words

Lewis base - asymmetric catalysis - Michael addition - aldehydes - quaternary carbon

    References and Notes

  • For recent reviews, see:
  • 1a Denissova I. Barriault L. Tetrahedron  2003,  59:  10105 
    Search in Google Scholar
  • 1b Douglas CJ. Overman LE. Proc. Natl. Acad. Sci. U.S.A.  2004,  101:  5363 
    Search in Google Scholar
  • 1c Trost BM. Chunhui J. Synthesis  2006,  369 
  • (d) For a recent monograph, see: Quaternary Stereocenters: Challenges and Solutions for Organic Synthesis   Christoffers J. Baro A. Wiley-VCH; Weinheim: 2005. 
  • For a recent example of a Michael addition reaction to set quaternary stereogenic centers, see:
  • 2a Kawato Y. Takahashi N. Kumagai N. Shibasaki M. Org. Lett.  2010,  12:  1484 
    Search in Google Scholar
  • For reviews, see:
  • 2b Jautze S. Peters R. Synthesis  2010,  365 
  • 2c

    Ref 1d, Chap. 4.

  • For reviews on catalytic, asymmetric Michael reactions, see:
  • 3a Tomioka K. Nagaoka Y. In Comprehensive Asymmetric Catalysis   Vol. 3:  Jacobsen EN. Pfaltz A. Yamamoto H. Springer; Berlin: 1999.  Chap. 31.1.
    Search in Google Scholar
  • 3b Kanai M. Shibasaki M. In Catalytic Asymmetric Synthesis   2nd ed.:  Ojima I. Wiley; New York: 2000.  p.569 
    Search in Google Scholar
  • 3c Sibi M. Manyem S. Tetrahedron  2000,  56:  8033 
    Search in Google Scholar
  • 3d Krause N. Hoffmann-Roder A. Synthesis  2001,  171 
  • 3e Christoffers J. Koripelly G. Rosiak A. Rossle M. Synthesis  2007,  1279 
  • 4 Bernardi A. Karamfilova K. Sanguinetti S. Scolastico C. Tetrahedron  1997,  53:  13009 
    CrossrefSearch in Google Scholar
  • For a discussion of these problems and potential solutions, see:
  • 5a Das JP. Chechik H. Marek I. Nature Chem.  2009,  1:  128 
    Search in Google Scholar
  • 5b Manthorpe JM. Gleason JL. J. Am. Chem. Soc.  2001,  123:  2091 
    Search in Google Scholar
  • 6a Narasaka K. Soai K. Mukaiyama T. Chem. Lett.  1974,  1223 
  • 6b Oare DA. Heathcock CA. In Topics in Stereochemistry   Vol. 20:  Eliel EL. Wilen SH. Wiley; New York: 1991.  p.125-170  
    Search in Google Scholar
  • 7 Takenaka N. Abell JP. Yamamoto H. J. Am. Chem. Soc.  2007,  129:  742 
    CrossrefSearch in Google Scholar
  • For leading references on catalytic, asymmetric synthesis of secondary and tertiary stereogenic centers using Lewis acid catalyzed MM reaction, see:
  • 8a Bernardi A. Colombo G. Scolastico C. Tetrahedron Lett.  1996,  37:  8921 
    Search in Google Scholar
  • 8b Kitajima H. Ito K. Katsuki T. Tetrahedron  1997,  53:  17015 
    Search in Google Scholar
  • 8c Kitajima H. Katsuki T. Synlett  1997,  568 
  • 8d Nishikori H. Ito K. Katsuki T. Tetrahedron: Asymmetry  1998,  9:  1165 
    Search in Google Scholar
  • 8e Evans DA. Rovis T. Kozlowski MC. Tedrow JS. J. Am. Chem. Soc.  1999,  121:  1994 
    Search in Google Scholar
  • 8f Evans DA. Willis MC. Johnston JN. Org. Lett.  1999,  1:  865 
    Search in Google Scholar
  • 8g Evans DA. Scheidt KA. Johnston JN. Willis MC. J. Am. Chem. Soc.  2001,  123:  4480 
    Search in Google Scholar
  • 8h Harada T. Iwai H. Takatsuki H. Fujita K. Kubo M. Oku A. Org. Lett.  2001,  3:  2101 
    Search in Google Scholar
  • 8i Desimoni G. Faita G. Filippone S. Mella M. Zampori MG. Zema M. Tetrahedron  2001,  57:  10203 
    Search in Google Scholar
  • 8j Wang X. Harada T. Iwai H. Oku A. Chirality  2003,  15:  28 
    Search in Google Scholar
  • 8k Wang X. Adachi S. Iwai H. Takatsuki H. Fujita K. Kubo M. Oku A. Harada T. J. Org. Chem.  2003,  68:  10046 
    Search in Google Scholar
  • 8l Suga H. Kitamura T. Kakehi A. Baba T. Chem. Commun.  2004,  1414 
  • 8m Ishihara K. Fushimi M. Org. Lett.  2006,  8:  1921 
    Search in Google Scholar
  • 8n Yang H. Kim S. Synlett  2008,  555 
  • For leading references on catalytic, asymmetric synthesis of secondary and tertiary stereogenic centers using organocatalyzed MM reactions, see:
  • 9a Brown SP. Goodwin NC. MacMillan DWC. J. Am. Chem. Soc.  2003,  125:  1192 
    Search in Google Scholar
  • 9b Wang W. Li H. Wang J. Org. Lett.  2005,  7:  1637 
    Search in Google Scholar
  • 9c Robichaud J. Tremblay F. Org. Lett.  2006,  8:  597 
    Search in Google Scholar
  • 9d Borths CJ. Carrera DE. MacMillan DWC. Tetrahedron  2009,  65:  6746 
    Search in Google Scholar
  • 10 For additions to aldehydes, see: Denmark SE. Wilson TW. Burk MT. Heemstra JR. J. Am. Chem. Soc.  2007,  129:  14864 
    CrossrefSearch in Google Scholar
  • 11 For additions to acid chlorides and anhydrides, see: Mermerian AH. Fu GC. Angew. Chem. Int. Ed.  2005,  44:  949 
    CrossrefSearch in Google Scholar
  • 12a Tennant G. In Comprehensive Organic Chemistry   Vol. 2:  Barton DHR. Olis WD. Sutherland IO. Pergamon; New York: 1979.  p.539-550  
    Search in Google Scholar
  • 12b Allen FH. Garner SE. In The Chemistry of Triple Bonded Functional Groups   Vol. 2:  Patai S. Wiley; New York: 1994. 
    Search in Google Scholar
  • 13 Cazeau P. Llonch J.-P. Simonin-Dabescat F. Frainnet E. J. Organomet. Chem.  1976,  105:  145 
    CrossrefSearch in Google Scholar
  • 14 For review of Lewis base catalysis, see: Denmark SE. Beutner GL. Angew. Chem. Int. Ed.  2008,  47:  1560 
    CrossrefPubMedSearch in Google Scholar
  • 15a Denmark SE. Wynn T. J. Am. Chem. Soc.  2001,  123:  6199 
    Search in Google Scholar
  • 15b Denmark SE. Wynn T. Beutner GL. J. Am. Chem. Soc.  2002,  124:  13405 
    Search in Google Scholar
  • 15c Denmark SE. Fan Y. J. Am. Chem. Soc.  2003,  125:  7825 
    Search in Google Scholar
  • 15d Denmark SE. Beutner GL. J. Am. Chem. Soc.  2003,  125:  7800 
    Search in Google Scholar
  • 15e Denmark SE. Heemstra JR. Org. Lett.  2003,  5:  2303 
    Search in Google Scholar
  • 15f Denmark SE. Heemstra JR. Synlett  2004,  13:  2411 
    Search in Google Scholar
  • 15g Denmark SE. Beutner GL. Wynn T. Eastgate MD. J. Am. Chem. Soc.  2005,  127:  3774 
    Search in Google Scholar
  • 15h Denmark SE. Fan Y. J. Org. Chem.  2005,  70:  9667 
    Search in Google Scholar
  • 15i Denmark SE. Bui T. J. Org. Chem.  2005,  70:  10190 
    Search in Google Scholar
  • 15j Denmark SE. Heemstra JR. J. Org. Chem.  2007,  72:  5668 
    Search in Google Scholar
  • 15k Denmark SE. Chung W.-J. J. Org. Chem.  2008,  73:  4582 
    Search in Google Scholar
  • 15l Denmark SE. Fujimori S. In Modern Aldol Reactions   Mahrwald R. Wiley-VCH; Weinheim: 2004.  Chap. 7.
  • 19 The amount of 15 mol% should equate to 1.73× the rate at 5 mol%, based on kinetic studies of the SiCl4/(R,R)-2 catalyst system, see: Denmark SE. Eklov BM. Yao PJ. Eastgate MD. J. Am. Chem. Soc.  2009,  131:  11770 
    CrossrefSearch in Google Scholar
  • 20 Previous studies have shown that trichlorosilyl enolates are competent nucleophiles for Lewis base catalyzed aldol additions, see: Denmark SE. Stavenger RA. J. Am. Chem. Soc.  2000,  122:  8837 
    CrossrefSearch in Google Scholar
16

See ref. 15j.

17

For recent preparation of SKIs, see ref .10.

18

For example, the observed selectivity could result from a single catalyst-enone complex if reaction through an achiral pathway was competitive with the catalyzed addition to form only one of the diastereomers.

21

The crystallographic coordinates of 7 have been deposited with the Cambridge Crystallographic Data Centre (CCDC); deposition no. 776146. These data can be obtained free of charge from the CCDC via www.ccdc.cam.ac.uk/data_request/cif.

22

For computational and mechanistic studies, see ref. 15g. For a full kinetic analysis, see ref. 19.