Direct Synthesis of Polybenzylated Glutamic Acid Monoesters: Disambiguation of N,N-Dibenzylglutamic Acid α- and γ-Benzyl Esters

Gastón Silveira-Dorta; Víctor S. Martín; José M. Padrón

doi:10.1055/s-0034-1378532

Synlett, Inhaltsverzeichnis

Synlett 2014; 25(15): 2166-2170
DOI: 10.1055/s-0034-1378532

letter

Direct Synthesis of Polybenzylated Glutamic Acid Monoesters: Disambiguation of N,N-Dibenzylglutamic Acid α- and γ-Benzyl Esters

Gastón Silveira-Dorta

Instituto Universitario de Bio-Orgánica ‘Antonio González’ (IUBO-AG), Centro de Investigaciones Biomédicas de Canarias (CIBICAN), Universidad de La Laguna, C/ Astrofísico Francisco Sánchez 2, 38206 La Laguna, Spain Fax: +34(922)318571 eMail: jmpadron@ull.es

,

Víctor S. Martín

Instituto Universitario de Bio-Orgánica ‘Antonio González’ (IUBO-AG), Centro de Investigaciones Biomédicas de Canarias (CIBICAN), Universidad de La Laguna, C/ Astrofísico Francisco Sánchez 2, 38206 La Laguna, Spain Fax: +34(922)318571 eMail: jmpadron@ull.es

,

José M. Padrón*

Instituto Universitario de Bio-Orgánica ‘Antonio González’ (IUBO-AG), Centro de Investigaciones Biomédicas de Canarias (CIBICAN), Universidad de La Laguna, C/ Astrofísico Francisco Sánchez 2, 38206 La Laguna, Spain Fax: +34(922)318571 eMail: jmpadron@ull.es

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Abstract

In this study, we explored the regioselective benzylation of l-glutamic acid under substoichiometric amounts of the alkylating agent. Our results demonstrate unambiguously that N,N-dibenzylglutamic acid γ-benzyl ester was not obtained by direct benzylation of l-glutamic acid as reported by other authors. Instead, under such reaction conditions N,N-dibenzylglutamic acid α-benzyl ester was obtained.

Key words

amino acids - benzylation - disambiguation - protecting groups - regioselectivity

Volltext

Referenzen

References

1a Padrón JM. Curr. Med. Chem. 2006; 13: 755
1b Padrón JM, Peters GJ. Invest. New Drugs 2006; 24: 195
1c Markidis T, Padrón JM, Martín VS, Peters GJ, Kokotos G. Anticancer Res. 2001; 21: 2835
1d Padrón JM, Martín VS, Hadjipavlou-Litina D, Noula C, Constantinou-Kokotou V, Peters GJ, Kokotos G. Bioorg. Med. Chem. Lett. 1999; 9: 821

2 Kokotos G, Padrón JM, Noula C, Gibbons WA, Martín VS. Tetrahedron: Asymmetry 1996; 7: 857

3a Kokotos G, Padrón JM, Martín T, Gibbons WA, Martín VS. J. Org. Chem. 1998; 63: 3741
3b Padrón JM, Kokotos G, Martín T, Markidis T, Gibbons WA, Martín VS. Tetrahedron: Asymmetry 1998; 9: 3381

4a Sutherland A, Caplan JF, Vederas JC. Chem. Commun. 1999; 555
4b Sutherland A, Vederas JC. Chem. Commun. 1999; 1739
4c Roche D, Prasad K, Repic O, Blacklock TJ. Tetrahedron Lett. 2001; 42: 1459
4d Adamczyk M, Reddy RE, Rege SD. J. Labelled Compd. Radiopharm. 2001; 44: 185
4e Hernández N, Martín VS. J. Org. Chem. 2001; 66: 4934
4f Constantinou-Kokotou V, Magrioti V, Markidis T, Kokotos G. J. Peptide Res. 2001; 58: 325
4g Magrioti V, Constantinou-Kokotou V. Lipids 2002; 37: 223
4h Wasserman HH, Long YO, Zhang R, Parr J. Heterocycles 2002; 58: 393
4i Constantinou-Kokotou V. Lett. Peptide Sci. 2002; 9: 143
4j Wasserman HH, Long YO, Zhang R, Parr J. Tetrahedron Lett. 2002; 43: 3351
4k Hanessian S, Angiolini M. Chem. Eur. J. 2002; 8: 111
4l Schleusner M, Gais H.-J, Koep S, Raabe G. J. Am. Chem. Soc. 2002; 124: 7789
4m Cox RJ, Gibson JS, Martín MB. M. ChemBioChem 2002; 3: 874
4n Gerwick WH, Leslie P, Long GC, Marquez BL, Willis CL. Tetrahedron Lett. 2003; 44: 285
4o Bycroft BW, Chhabra SR, Kellam B, Smith P. Tetrahedron Lett. 2003; 44: 973
4p Abraham A, Howarth NM. Nucleosides, Nucleotides Nucleic Acids 2003; 22: 675
4q Gorohovsky S, Meir S, Shkoulev V, Byk G, Gellerman G. Synlett 2003; 1411
4r Hallinan EA, Hagen TJ, Bergmanis A, Moore WM, Jerome GM, Spangler DP, Stevens AM, Shieh HS, Manning PT, Pitzele BS. J. Med. Chem. 2004; 47: 900
4s Hamilton DJ, Sutherland A. Tetrahedron Lett. 2004; 45: 5739
4t Shin H, Cama E, Christianson DW. J. Am. Chem. Soc. 2004; 126: 10278
4u Haug BE, Rich DH. Org. Lett. 2004; 6: 4783
4v Gallos JK, Sarli VC, Massen ZS, Varvogli AC, Papadoyanni CZ, Papaspyrou SD, Argyropoulos NG. Tetrahedron 2005; 61: 565

5 Silveira-Dorta G, Donadel OJ, Martín VS, Padrón JM. J. Org. Chem. 2014; 79: 6775
6 Rodriquez M, Taddei M. Synthesis 2005; 493

7a Minassian F. C. R. Chimie 2005; 8: 859
7b Rodriquez M, Bruno I, Cini E, Marchetti M, Taddei M, Gomez-Paloma L. J. Org. Chem. 2006; 71: 103
7c Rodriquez M, Terracciano S, Cini E, Settembrini G, Bruno I, Bifulco G, Taddei M, Gomez-Paloma L. Angew. Chem. Int. Ed. 2006; 45: 423
7d Le Quement ST, Nielsen TE, Meldal M. J. Comb. Chem. 2007; 9: 1060
7e Dzhekieva L, Rocaboy M, Kerff F, Charlier P, Sauvage E, Pratt RF. Biochemistry 2010; 49: 6411
7f Culhane JC, Wang D, Yen PM, Cole PA. J. Am. Chem. Soc. 2010; 132: 3164
7g Botta CB, Cabri W, Cini E, De Cesare L, Fattorusso C, Giannini G, Persico M, Petrella A, Rondinelli F, Rodriquez M, Russo A, Taddei M. J. Med. Chem. 2011; 54: 2165

8a Oestreich M, Fröhlich R, Hoppe D. Tetrahedron Lett. 1988; 39: 1745
8b Kikuchi H, Yamamoto K, Horoiwa S, Hirai S, Kasahara R, Hariguchi N, Matsumoto M, Oshima Y. J. Med. Chem. 2006; 49: 4698

9 Albert R, Danklmaier J, Hönig H, Kandolf H. Synthesis 1987; 635

10a Kuntiyong P, Akkarasamiyo S, Eksinitkun E. Chem. Lett. 2006; 35: 1008
10b Kuntiyong P, Akkarasamiyo S, Piboonsrinakara N, Hemmara C, Songthammawat P. Tetrahedron 2011; 67: 8034

11 Akkarasamiyo S. PhD Thesis 2008; 28-29 ; accessible at http://www.thapra.lib.su.ac.th/objects/thesis/fulltext/snamcn/Sunisa_Akkarasamiyo/Fulltext.pdf (last accessed Aug 1, 2014); Silpakorn University, Thailand

Zusatzmaterial

Supporting Information