Synthesis 2003(14): 2179-2184  
DOI: 10.1055/s-2003-41057
PAPER
© Georg Thieme Verlag Stuttgart · New York

Detritylation Procedure under Non-Acidic Conditions: Naphthalene Catalysed­ Reductive Cleavage of Trityl Ethers

Miguel Yus*, Cherif Behloul, David Guijarro
Departamento de Química Orgánica, Facultad de Ciencias, Universidad de Alicante, Apdo. 99, 03080 Alicante, Spain
Fax: +34(96)5903549; e-Mail: yus@ua.es;
Further Information

Publication History

Received 30 June 2003
Publication Date:
24 September 2003 (online)

Abstract

The reaction of primary, secondary, allylic and benzylic trityl ethers 1 with lithium powder and a catalytic amount of naphthalene led to reductive cleavage of the trityl-oxygen bond, affording the corresponding alcohols 2 in good to excellent yields under very mild reaction conditions. The detritylation process could successfully be extended to several hydroxy, alkoxy and amino functionalised trityl ethers. This methodology represents a new and efficient detritylation procedure under non-acidic reaction conditions.

    References

  • 1a Helferich B. Adv. Carbohydr. Chem.  1948,  3:  79 
  • 1b Dekker CA. Goodman L. In Chemistry and Biochemistry   Vol. IIA:  Pigman W. Horton D. Academic Press; New York: 1970.  p.22 
  • 2a Bodanszky M. Onetti OA. Peptide Synthesis   Interscience; New York: 1966.  p.36 
  • 2b Bodanszky M. Principles in Peptide Synthesis   Springer-Verlag; New York: 1993.  2nd ed.. p.88 
  • 3 Köster H. Hoppe N. Kohli V. Kröpelin M. Kaut H. Kulikowski K. Nucleic Acids Symp. Ser.  1980,  7:  39 
  • 4 Greene TW. Wuts PGM. Protective Groups in Organic Synthesis   John Wiley & Sons; New York: 1999.  p.103 
  • 5 Kunz H. Waldmann H. In Comprehensive Organic Synthesis   Vol. 6:  Trost BM. Pergamon Press; Oxford: 1991.  p.650 
  • 6 Imagawa H. Tsuchihashi T. Singh RK. Yamamoto H. Sugihara T. Nishizawa M. Org. Lett.  2003,  5:  153 
  • 7 Rele S. Nayak SK. Synth. Commun.  2002,  32:  3533 
  • 8 Hwu JR. Jain ML. Tsai F.-Y. Tsay S.-C. Balakumar A. Hakimelahi GH. J. Org. Chem.  2000,  65:  5077 
  • For reviews see:
  • 9a Yus M. Chem. Soc. Rev.  1996,  25:  155 
  • 9b Ramón DJ. Yus M. Eur. J. Org. Chem.  2000,  225 
  • 9c Yus M. Synlett  2001,  1197 
  • 9d Yus M. Ramón DJ. Latv. J. Chem.  2002,  79 
  • 9e Ramón DJ. Yus M. Rev. Cubana Quim.  2002,  14:  76 
  • 9f Yus M. In The Chemistry of Organolithium Compounds   Rappoport Z. Mareck I. J. Wiley & Sons; Chichester: 2003. 
  • 9g For a mechanistic study see: Yus M. Herrera RP. Guijarro A. Tetrahedron Lett.  2001,  42:  3455 
  • 9h See also: Yus M. Herrera RP. Guijarro A. Chem.-Eur. J.  2002,  8:  2574 
  • 9i See also: Herrera RP. Guijarro A. Yus M. Tetrahedron Lett.  2003,  44:  1309 
  • For a polymer-supported version of this reaction see:
  • 10a Gómez C. Ruiz S. Yus M. Tetrahedron Lett.  1998,  39:  1397 
  • 10b Gómez C. Ruiz S. Yus M. Tetrahedron  1999,  55:  7017 
  • 10c Yus M. Gómez C. Candela P. Tetrahedron  2002,  58:  6207 
  • 11 For a review see: Guijarro D. Yus M. Recent Res. Dev. Org. Chem.  1998,  2:  713 
  • For reviews see:
  • 12a Nájera C. Yus M. Trends Org. Chem.  1991,  2:  155 
  • 12b Nájera C. Yus M. Recent Res. Dev. Org. Chem.  1997,  1:  67 
  • 12c Nájera C. Yus M. Curr. Org. Chem.  2003,  7:  867 
  • 13 For a review see: Yus M. Foubelo F. Rev. Heteroatom Chem.  1997,  17:  73 
  • 14a Guijarro D. Mancheño B. Yus M. Tetrahedron  1992,  48:  4593 
  • 14b Guijarro D. Mancheño B. Yus M. Tetrahedron Lett.  1992,  33:  5597 
  • 14c Guijarro D. Guillena G. Mancheño B. Yus M. Tetrahedron  1994,  50:  3427 
  • 14d Guijarro D. Mancheño B. Yus M. Tetrahedron  1994,  50:  8551 
  • 14e Guijarro D. Yus M. Tetrahedron  1995,  51:  11445 
  • 14f Alonso E. Guijarro D. Yus M. Tetrahedron  1995,  51:  11457 
  • 14g Alonso E. Ramón DJ. Yus M. J. Org. Chem.  1997,  62:  417 
  • 14h Alonso E. Ramón DJ. Yus M. Tetrahedron  1997,  53:  14355 
  • 14i Alonso E. Guijarro D. Martínez P. Ramón DJ. Yus M. Tetrahedron  1999,  55:  11027 
  • 15 For a review on the cleavage of ethers with organoalkali metal compounds and alkali metals see: Maercker A. Angew. Chem., Int. Ed. Engl.  1987,  26:  972 
  • 16 The formation of orange-red solutions of the trityl radical in THF has been described in the literature. See for instance: Ashby EC. Goel AB. DePriest RN. J. Org. Chem.  1981,  46:  2429 
  • For reviews on CIPE see:
  • 17a Beak P. Meyers AI. Acc. Chem. Res.  1986,  19:  356 
  • 17b Snieckus V. Chem. Rev.  1990,  90:  879 
  • 17c Beak P. Basu A. Gallagher DJ. Park YS. Thayumanavan S. Acc. Chem. Res.  1996,  29:  552 
  • 18 Yus M. Martinez P. Guijarro D. Tetrahedron  2001,  57:  10119 
  • 19 Watson SC. Eastham JF. J. Organomet. Chem.  1967,  9:  165 
  • 20 Colin-Messager S. Girard J.-P. Rossi J.-C. Tetrahedron Lett.  1992,  33:  2689 
  • 21 Chaudhary SK. Hernández O. Tetrahedron Lett.  1979,  95 
  • 22 Freeman PK. Siggel L. Chamberlain PH. Clapp GE. Tetrahedron  1988,  44:  5051 
  • 23 Jones GB. Huber RS. Chapman BJ. Tetrahedron: Asymmetry  1997,  8:  1797 
  • 24 Carganico G, Mauleón Casellas D, and García Pérez ML. inventors; PCT Int. Appl. WO  9428004.  1994; Chem. Abstr. 1994, 123: 170071