Synthesis 2004(8): 1274-1280  
DOI: 10.1055/s-2004-822358
PAPER
© Georg Thieme Verlag Stuttgart · New York

Detritylation of N-Tritylamines via a Naphthalene-Catalyzed Lithiation Process

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

Publication History

Received 23 February 2004
Publication Date:
03 May 2004 (online)

Abstract

The reaction of aliphatic and aromatic secondary and tertiary N-tritylamines 1 with lithium powder and a catalytic amount of naphthalene led to reductive detritylation, affording the corresponding amines 2 in good to excellent yields. The trityl group could selectively be removed in the presence of an allyl or a benzyl group. The detritylation process could successfully be extended to several hydroxy, alkoxy and amino functionalized N-tritylamines. The chemoselectivity between the trityl-nitrogen and the trityl-oxygen bond cleavages was also studied. This methodology represents an efficient deprotection of N-tritylamines under nonacidic reaction conditions.

    References

  • 1a Sheppard RC. In Comprehensive Organic Chemistry   Vol. 5:  Barton D. Ollis WD. Pergamon; Oxford: 1979.  p.323 
  • 1b Kunz H. Waldmann H. In Comprehensive Organic Synthesis   Vol. 6:  Trost BM. Fleming I. Pergamon; Oxford: 1991.  p.644 
  • 1c Greene TW. Wuts PGM. Protective Groups in Organic Synthesis   Wiley; New York: 1999.  p.583 
  • 2a Bodanszky M. Onetti OA. Peptide Synthesis   Wiley Interscience; New York: 1966.  p.36 
  • 2b Bodanszky M. Principles in Peptide Synthesis   Springer-Verlag; New York: 1993.  2nd ed.. p.88 
  • 3 See, for instance: Applegate HE. Cimarusti CM. Dolfini JE. Funke PT. Koster WH. Puar MS. Slusarchyk WA. Young MG. J. Org. Chem.  1979,  44:  811 
  • 4 See, for instance: Sharma SK. Songster MF. Colpitts TL. Hegyes P. Barany G. Castellino FJ. J. Org. Chem.  1993,  58:  4993 
  • 5 Maltese M. J. Org. Chem.  2001,  66:  7615 
  • 6 Vedejs E. Klapars A. Warner DL. Weiss AH. J. Org. Chem.  2001,  66:  7542 
  • 7 Rele S. Nayak SK. Synth. Commun.  2002,  32:  3533 
  • 8 Chandrasekhar S. Nagendra Babu B. Reddy CR. Tetrahedron Lett.  2003,  44:  2057 
  • 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. Wiley; Chichester: 2004.  Chap. 11.
  • 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 
  • 12d Nájera C. Sansano JM. Yus M. Tetrahedron  2003,  59:  9255 
  • 12e Chinchilla R. Nájera C. Yus M. Chem. Rev.  2004,  in press 
  • For reviews, see:
  • 13a Yus M. Foubelo F. Rev. Heteroatom. Chem.  1997,  17:  73 
  • 13b Yus M. Foubelo F. Targets Heterocycl. Syst.  2002,  6:  136 
  • 13c Yus M. Pure Appl. Chem.  2003,  75:  1453 
  • 14a Almena J. Foubelo F. Yus M. J. Org. Chem.  1994,  59:  3210 
  • 14b Almena J. Foubelo F. Yus M. Tetrahedron  1994,  50:  5775 
  • 14c Almena J. Foubelo F. Yus M. Tetrahedron  1996,  52:  8545 
  • 14d Alonso E. Guijarro D. Martínez P. Ramón DJ. Yus M. Tetrahedron  1999,  55:  11027 
  • 14e Guijarro D. Martínez PJ. Nájera C. Yus M. ARKIVOC [Online] 2004,  Part(iv):  5 ; www.arkat-usa.org
  • 15 Yus M. Behloul C. Guijarro D. Synthesis  2003,  2179 
  • 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 
  • 17 Chadwick DJ. Hodgson ST. J. Chem. Soc., Perkin Trans. 1  1983,  93 
  • 18 Yus M. Martinez P. Guijarro D. Tetrahedron  2001,  57:  10119 
  • 19 Watson SC. Eastham JF. J. Organomet. Chem.  1967,  9:  165 
  • 20 Chandrasekhar S. Babu BN. Reddy CR. Tetrahedron Lett.  2003,  44:  2057 
  • 21 Boyce CBC. Milborrow BV. Nature  1965,  208:  537 
  • 22 Roth HJ. Kallmeyer G. Arch. Pharm. (Weinheim)  1988,  321:  273 ; Chem. Abstr. 1989, 110, 57263