Download PDF
Synthesis 2009(2): 335-338  
DOI: 10.1055/s-0028-1083275
PSP
© Georg Thieme Verlag Stuttgart ˙ New York

Enantioselective Rhodium-Catalyzed Alkylative Desymmetrization of 3,5-Dimethylglutaric Anhydride

Matthew J. Cook, Tomislav Rovis*
Department of Chemistry, Colorado State University, Fort Collins, CO 80523, USA
Fax: +1(970)4911801; e-Mail: rovis@lamar.colostate.edu;
Further Information

Publication History

Received 16 June 2008
Publication Date:
12 December 2008 (online)

    Permissions and Reprints All articles of this category

Abstract

A rhodium-catalyzed enantioselective cross-coupling of sp³ organozinc reagents and 3,5-dimethylglutaric anhydride has been developed to afford the corresponding products, syn-deoxypolypropionates, in excellent yields and enantioselectivities. This reaction has been developed so that both commercially available and in situ prepared organozinc reagents are competent coupling partners.

Key words

organozinc reagents - Grignard reagents - C-C bond formation - syn-deoxypolypropionates

    References

  • Reviews:
  • 1a Willis MC. J. Chem. Soc., Perkin Trans. 1  1999,  1765 
    Google Scholar
  • 1b Rovis T. Recent Advances in Catalytic Asymmetric Desymmetrization Reactions, In New Frontiers in Asymmetric Catalysis   Mikami K. Lautens M. Wiley; New York: 2007.  p.275-312  
    Google Scholar
  • 1c Atodiresei I. Schiffers I. Bolm C. Chem. Rev.  2007,  107:  5683 
    Google Scholar
  • For reviews including the asymmetric alcoholysis of cyclic anhydrides, see:
  • 2a Cheng Y. McDaid P. Deng L. Chem. Rev.  2003,  103:  2965 
    Google Scholar
  • 2b Tian S.-K. Chen Y. Hang J. Tang L. McDaid P. Deng L. Acc. Chem. Res.  2004,  37:  621 
    Google Scholar
  • For asymmetric arylation of glutaric anhydrides using stoichiometric quantities of sparteine, see:
  • 2c Shintani R. Fu GC. Angew. Chem. Int. Ed.  2002,  41:  1057 
    Google Scholar
  • 3a Bercot EA. Rovis T. J. Am. Chem. Soc.  2002,  124:  174 
    Google Scholar
  • 3b Bercot EA. Rovis T. J. Am. Chem. Soc.  2005,  127:  247 
    Google Scholar
  • 3c Johnson JB. Yu RT. Fink P. Bercot EA. Rovis T. Org. Lett.  2006,  8:  4307 
    Google Scholar
  • 3d Johnson JB. Bercot EA. Rowley JM. Coates GW. Rovis T. J. Am. Chem. Soc.  2007,  129:  2718 
    Google Scholar
  • 3e Rogers RL. Moore JL. Rovis T. Angew. Chem. Int. Ed.  2007,  46:  9301 
    Google Scholar
  • 3f Johnson JB. Rovis T. Acc. Chem. Res.  2008,  41:  327 
    Google Scholar
  • For other contributions to anhydride activation, see:
  • 4a Jabri N. Alexakis A. Normant JF. Tetrahedron  1986,  42:  1369 
    Google Scholar
  • 4b Frost CG. Wadsworth KJ. Chem. Commun.  2001,  2316 
    Google Scholar
  • 4c Goossen LJ. Ghosh K. Angew. Chem. Int. Ed.  2001,  40:  3458 
    Google Scholar
  • 4d Goossen LJ. Ghosh K. Eur. J. Org. Chem.  2002,  3254 
    Google Scholar
  • 4e Cacchi S. Fabrizi G. Gavazza F. Goggiamani A. Org. Lett.  2003,  5:  289 
    Google Scholar
  • 4f Wang D. Zhang Z. Org. Lett.  2003,  5:  4645 
    Google Scholar
  • 4g Yamane M. Uera K. Narasaka K. Chem. Lett.  2004,  33:  424 
    Google Scholar
  • 4h Kazmierski I. Bastienne M. Gosmini C. Paris J.-M. Perichon J. J. Org. Chem.  2004,  69:  936 
    Google Scholar
  • 4i Xin B. Zhang Y. Cheng K. J. Org. Chem.  2006,  71:  5725 
    Google Scholar
  • 4j Oguma K. Miura M. Satoh T. Nomura M. J. Organomet. Chem.  2002,  648:  297 
    Google Scholar
  • 4k Hong Y.-T. Barchuk A. Krische MJ. Angew. Chem. Int. Ed.  2006,  45:  6885 
    Google Scholar
  • 5 Bercot EA. Rovis T. J. Am. Chem. Soc.  2004,  126:  10248 
    CrossrefGoogle Scholar
  • 6 Johnson JB. Bercot EA. Williams CM. Rovis T. Angew. Chem. Int. Ed.  2007,  46:  4514 
    CrossrefGoogle Scholar
  • 7 Hanessian S. Giroux S. Mascitti V. Synthesis  2006,  1057 
    Article in Thieme ConnectGoogle Scholar
  • 8a von Matt P. Pfaltz A. Angew. Chem., Int. Ed. Engl.  1993,  32:  566 
    Google Scholar
  • 8b Sprinz J. Helmchen G. Tetrahedron Lett.  1993,  34:  1769 
    Google Scholar
  • 8c Dawson GJ. Frost CG. Williams JMJ. Coote SJ. Tetrahedron Lett.  1993,  34:  3149 
    Google Scholar
  • 8d Review: Helmchen G. Pfaltz A. Acc. Chem. Res.  2000,  33:  336 
    Google Scholar
  • 10 For nucleophiles formed by direct Zn-I exchange; see: Rozema MJ. Achyuta Rao S. Knochel P. J. Org. Chem.  1992,  57:  1956 
    CrossrefGoogle Scholar
  • 11 Cook MJ. Rovis T. J. Am. Chem. Soc.  2007,  129:  9302 
    CrossrefGoogle Scholar
  • 12 Patel DV. VanMiddlesworth F. Donaubauer J. Gannett P. Sih CJ. J. Am. Chem. Soc.  1986,  108:  4603 
    CrossrefGoogle Scholar
9

The reaction proceeds in a cleaner fashion if the Grignard is prepared in situ, to avoid by-products arising from oxidation of the organometallic.