Download PDF
Synthesis 2007(21): 3411-3420  
DOI: 10.1055/s-2007-990835
FEATUREARTICLE
© Georg Thieme Verlag Stuttgart · New York

Electrochemistry and Umpolung Reactions: New Tools for Solving Synthetic Challenges of Structure and Location

Feili Tang, Ceng Chen, Kevin D. Moeller*
Department of Chemistry, Washington University, St. Louis, MO 63130, USA
Fax: +1(314)9354481; e-Mail: moeller@wustl.edu;
Further Information

Publication History

Received 3 September 2007
Publication Date:
16 October 2007 (online)

    Permissions and Reprints All articles of this category

Abstract

Electrochemistry is a powerful tool for initiating new umpolung reactions. In this paper, two examples are provided. One demonstrates the use of electrochemistry for reversing the polarity of known functional groups and triggering carbon-carbon bond formation. The second demonstrates the use of electrochemistry for reversing the polarity of a chemical reagent, a technique that allows for spatially locating synthetic transformations on addressable chips.

Key words

electron transfer - umpolung - cyclizations - site-selective reactions - Heck reactions

    References

  • For a recent review see:
  • 1a Sperry JB. Wright DL. Chem. Soc. Rev.  2006,  35:  605 
    CrossrefPubMedGoogle Scholar
  • For an extensive discussion of electrochemistry as a synthetic tool see:
  • 1b Organic Electrochemistry   4th ed.:  Lund H. Hammerich O. Dekker; New York: 2001. 
    CrossrefPubMedGoogle Scholar
  • 2a Nielsen MF. Utley JHP. Reductive Coupling In Organic Electrochemistry   4th ed.:  Lund H. Hammerich O. Dekker; New York: 2001. 
    Google Scholar
  • 2b Little RD. Schwaebe MK. Top. Curr. Chem.  1996,  185:  1-48  
    Google Scholar
  • 2c For summaries of recent work see ref. 1a and: Little RD. Moeller KD. Electrochem. Soc. Interface  2002,  11:  36 
    Google Scholar
  • For a reviews see:
  • 3a Moeller KD. Tetrahedron  2000,  56:  9527 
    Google Scholar
  • 3b Moeller KD. Top. Curr. Chem.  1996,  185:  49-86  ; in addition to ref. 1a above
    Google Scholar
  • For a review of early work see ref. 3a. For recent work see:
  • 4a Huang Y. Moeller KD. Tetrahedron  2006,  62:  6536 
    CrossrefGoogle Scholar
  • 4b Brandt JD. Moeller KD. Org. Lett.  2005,  7:  3553 ; and references cited therein
    CrossrefGoogle Scholar
  • 5 Mihelcic J. Moeller KD. J. Am. Chem. Soc.  2004,  126:  9106 
    CrossrefPubMedGoogle Scholar
  • 6 Frey DA. Wu N. Moeller KD. Tetrahedron Lett.  1996,  37:  8317 
    CrossrefGoogle Scholar
  • 7 Wright DL. Whitehead CR. Sessions EH. Ghiviriga I. Frey DA. Org. Lett.  1999,  1:  1535 
    CrossrefGoogle Scholar
  • 8a Hughes CC. Miller AK. Trauner D. Org. Lett.  2005,  7:  3425 
    CrossrefPubMedGoogle Scholar
  • 8b Miller AK. Hughes CC. Kennedy-Smith JJ. Gradl SN. Trauner D. J. Am. Chem. Soc.  2006,  128:  17057 
    CrossrefPubMedGoogle Scholar
  • 9 Frey DA. Reddy SHK. Wu N. Moeller KD. J. Org. Chem.  1999,  64:  2805 
    CrossrefGoogle Scholar
  • 10a Sutterer AC. Moeller KD. J. Am. Chem. Soc.  2000,  122:  5636 
    CrossrefPubMedGoogle Scholar
  • 10b Duan S. Moeller KD. Org. Lett.  2001,  3:  2685 
    CrossrefPubMedGoogle Scholar
  • 10c Duan S. Moeller KD. J. Am. Chem. Soc.  2002,  124:  9368 
    CrossrefPubMedGoogle Scholar
  • 10d Liu B. Duan S. Sutterer AC. Moeller KD. J. Am. Chem. Soc.  2002,  124:  10101 
    CrossrefPubMedGoogle Scholar
  • 11a Organic Electrochemistry   4th ed.:  Lund H. Hammerich O. Dekker; New York: 2001.  p.44 
    Google Scholar
  • 11b Yoshida KI. Electrooxidation in Organic Chemistry: The Role of Cation Radical Intermediates   John Wiley & Sons; New York: 1984.  p.13 
    Google Scholar
  • 11c Fry AJ. Synthetic Organic Electrochemistry   2nd ed.:  John Wiley & Sons; New York: 1989.  p.37 
    Google Scholar
  • 12 For a description of the ‘1 K chips’ used here, see: Dill K. Montgomery DD. Wang W. Tsai JC. Anal. Chim. Acta  2001,  444:  69 ; electrode diameter = 92 µM; distance between the Pt electrodes (rectangular cells) = 245.3 µM and 337.3 µM
    CrossrefGoogle Scholar
  • For the use of acid on the chips see:
  • 13a Rossi FM, and Montgomery DD. inventors; WO  0053625. 
    CrossrefGoogle Scholar
  • 13b Maurer K. McShea A. Strathmann M. Dill K. J. Comb. Chem.  2005,  7:  637 
    CrossrefGoogle Scholar
  • For Pd(II) reactions see:
  • 14a Tesfu E. Roth K. Maurer K. Moeller KD. Org. Lett.  2006,  8:  709 
    CrossrefGoogle Scholar
  • 14b Tesfu E. Maurer K. Ragsdale SR. Moeller KD. J. Am. Chem. Soc.  2004,  126:  6212 
    CrossrefGoogle Scholar
  • 14c Tesfu E. Maurer K. McShae A. Moeller KD. J. Am. Chem. Soc.  2006,  128:  70 
    CrossrefGoogle Scholar
  • 15 For a Pd(0) reaction see: Tian J. Maurer K. Tesfu E. Moeller KD. J. Am. Chem. Soc.  2005,  127:  1392 
    CrossrefGoogle Scholar
  • 16 Maurer K. inventors; US  2007065877. For a base-cleavable linker, see:
  • 17 This procedure followed the work of: Smith AB. Lupo AT. Ohba M. Chen K. J. Am. Chem. Soc.  1989,  111:  6648 
    CrossrefGoogle Scholar