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

Cherif Behloul; David Guijarro; Miguel Yus

doi:10.1055/s-2004-822358

Subscribe to RSS

Please copy the URL and add it into your RSS Feed Reader.

https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000084.xml

Share / Bookmark

Facebook X Linkedin Weibo

Download PDF

Synthesis 2004(8): 1274-1280
DOI: 10.1055/s-2004-822358

PAPER

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
Full Text
References

Permissions and Reprints All articles of this category

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.

Key words

tritylamine - lithium - lithiation - detritylation - reductive cleavage

References

1a Sheppard RC. In Comprehensive Organic Chemistry Vol. 5: Barton D. Ollis WD. Pergamon; Oxford: 1979. p.323

Google Scholar
1b Kunz H. Waldmann H. In Comprehensive Organic Synthesis Vol. 6: Trost BM. Fleming I. Pergamon; Oxford: 1991. p.644

Google Scholar
1c Greene TW. Wuts PGM. Protective Groups in Organic Synthesis Wiley; New York: 1999. p.583

Google Scholar
2a Bodanszky M. Onetti OA. Peptide Synthesis Wiley Interscience; New York: 1966. p.36

Google Scholar
2b Bodanszky M. Principles in Peptide Synthesis Springer-Verlag; New York: 1993. 2nd ed.. p.88

Google Scholar
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

Crossref Google Scholar
4 See, for instance: Sharma SK. Songster MF. Colpitts TL. Hegyes P. Barany G. Castellino FJ. J. Org. Chem. 1993, 58: 4993

Crossref Google Scholar
5 Maltese M. J. Org. Chem. 2001, 66: 7615

Crossref Google Scholar
6 Vedejs E. Klapars A. Warner DL. Weiss AH. J. Org. Chem. 2001, 66: 7542

Crossref Google Scholar
7 Rele S. Nayak SK. Synth. Commun. 2002, 32: 3533

Crossref Google Scholar
8 Chandrasekhar S. Nagendra Babu B. Reddy CR. Tetrahedron Lett. 2003, 44: 2057

Crossref Google Scholar
For reviews, see:
9a Yus M. Chem. Soc. Rev. 1996, 25: 155

Crossref Google Scholar
9b Ramón DJ. Yus M. Eur. J. Org. Chem. 2000, 225

Crossref Google Scholar
9c Yus M. Synlett 2001, 1197

Crossref Google Scholar
9d Yus M. Ramón DJ. Latv. J. Chem. 2002, 79

Crossref Google Scholar
9e Ramón DJ. Yus M. Rev. Cubana Quim. 2002, 14: 76

Crossref Google Scholar
9f Yus M. In The Chemistry of Organolithium Compounds Rappoport Z. Mareck I. Wiley; Chichester: 2004. Chap. 11.

Crossref Google Scholar
9g For a mechanistic study, see: Yus M. Herrera RP. Guijarro A. Tetrahedron Lett. 2001, 42: 3455

Crossref Google Scholar
9h See also: Yus M. Herrera RP. Guijarro A. Chem. Eur. J. 2002, 8: 2574

Crossref Google Scholar
9i See also: Herrera RP. Guijarro A. Yus M. Tetrahedron Lett. 2003, 44: 1309

Crossref Google Scholar
For a polymer-supported version of this reaction, see:
10a Gómez C. Ruiz S. Yus M. Tetrahedron Lett. 1998, 39: 1397

Crossref Google Scholar
10b Gómez C. Ruiz S. Yus M. Tetrahedron 1999, 55: 7017

Crossref Google Scholar
10c Yus M. Gómez C. Candela P. Tetrahedron 2002, 58: 6207

Crossref Google Scholar
11 For a review, see: Guijarro D. Yus M. Recent Res. Dev. Org. Chem. 1998, 2: 713

Google Scholar
For reviews, see:
12a Nájera C. Yus M. Trends Org. Chem. 1991, 2: 155

Google Scholar
12b Nájera C. Yus M. Recent Res. Dev. Org. Chem. 1997, 1: 67

Google Scholar
12c Nájera C. Yus M. Curr. Org. Chem. 2003, 7: 867

Google Scholar
12d Nájera C. Sansano JM. Yus M. Tetrahedron 2003, 59: 9255

Google Scholar
12e Chinchilla R. Nájera C. Yus M. Chem. Rev. 2004, in press

Google Scholar
For reviews, see:
13a Yus M. Foubelo F. Rev. Heteroatom. Chem. 1997, 17: 73

Crossref Google Scholar
13b Yus M. Foubelo F. Targets Heterocycl. Syst. 2002, 6: 136

Crossref Google Scholar
13c Yus M. Pure Appl. Chem. 2003, 75: 1453

Crossref Google Scholar
14a Almena J. Foubelo F. Yus M. J. Org. Chem. 1994, 59: 3210

Google Scholar
14b Almena J. Foubelo F. Yus M. Tetrahedron 1994, 50: 5775

Google Scholar
14c Almena J. Foubelo F. Yus M. Tetrahedron 1996, 52: 8545

Google Scholar
14d Alonso E. Guijarro D. Martínez P. Ramón DJ. Yus M. Tetrahedron 1999, 55: 11027

Google Scholar
14e Guijarro D. Martínez PJ. Nájera C. Yus M. ARKIVOC [Online] 2004, Part(iv): 5 ; www.arkat-usa.org

Google Scholar
15 Yus M. Behloul C. Guijarro D. Synthesis 2003, 2179

Article in Thieme Connect Google Scholar
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

Crossref Google Scholar
17 Chadwick DJ. Hodgson ST. J. Chem. Soc., Perkin Trans. 1 1983, 93

Crossref Google Scholar
18 Yus M. Martinez P. Guijarro D. Tetrahedron 2001, 57: 10119

Crossref Google Scholar
19 Watson SC. Eastham JF. J. Organomet. Chem. 1967, 9: 165

Crossref Google Scholar
20 Chandrasekhar S. Babu BN. Reddy CR. Tetrahedron Lett. 2003, 44: 2057

Crossref Google Scholar
21 Boyce CBC. Milborrow BV. Nature 1965, 208: 537

Google Scholar
22 Roth HJ. Kallmeyer G. Arch. Pharm. (Weinheim) 1988, 321: 273 ; Chem. Abstr. 1989, 110, 57263

Google Scholar