Synthesis of Nitrogen–, Oxygen– and Sulphur–containing Tripodal Ligands with a Trimethylbenzene Core

Heraclio López–Ruiz,¹* Mayra Cortés–Hernández,¹ Susana Rojas–Lima,¹ and Herbert Höpfl²

¹ Área Académica de Química, Universidad Autónoma del Estado de Hidalgo, Carretera Pachuca–Tulancingo Km. 4.5, Ciudad Universitaria, C.P. 42184 Mineral de la Reforma, Hidalgo, México. *heraclio@uaeh.edu.mx

² Centro de Investigaciones Químicas, Universidad Autónoma del Estado de Morelos, Avenida Universidad 1001, C.P. 62209 Cuernavaca, Morelos, México.

Received September 24, 2010. ]]> Accepted March 31, 2011.

Abstract

Synthetic procedures for the preparation of various nitrogen–, oxygen– and sulphur–containing tripodal ligands having a 1,3,5–trimethylbenzene core are reported.

Keywords: 1,3,5–tris(bromomethyl)benzene, ethyl–xanthate, tris–thiol, tripodal ligands, Michael additions, ligand design.

Resumen

Se describe la preparación de diferentes ligantes tripodales que contienen átomos de nitrógeno, oxígeno y azufre, así como la plataforma 1,3,5–trimetilbenceno.

Palabras clave: 1,3,5–tris(bromometil)benceno, etilxantato, tris–tiol, ligandos tripodales, adiciones de Michael, diseño de ligantes.

Acknowledgments

We are indebted to Conacyt, for financial support via grants J49336–Q and 84453. We are indebted to Prof. Joseph M. Muchowski for many friendly discussions.

References:

1. Hennrich, G.; Anslyn, E. V. Chem. Eur. J. 2002, 8, 2219–2224.         [ Links ]

2. Lehn, J.–M. Supramolecular Reactivity and Catalysis of Phosphoryl Transfer. In Bioorganic Chemistry in Healthcare and Technology; Pandit, U. K., Alderweireldt, F. C., Eds.; Plenum Press: New York, 1991.         [ Links ]

3. a) Snyder, L. R.; Glajch, J. L.; Kirkland, J. J. Practical HPLC Method Development, Wiley & Sons: New York, 1988.         [ Links ] b) Schmidtchen, F. P. Nachr. Chem. Tech. Lab. 1988, 36, 8–12.         [ Links ]

4. a) Yang, X.; Knobler, C. B.; Hawthorne, M. F. Angew. Chem., Int. Ed. Engl. 1991, 30, 1507–1508.         [ Links ] b) Arunachalam, M.; Ghosh, P. Inorg Chem. 2010, 49, 943–951.         [ Links ] c) Singh, A. S.; Chen, B. Y.; Wen, Y.–S.; Tsai, C.; Sun, S.–S. Org. Lett. 2009, 11, 1867–1870.         [ Links ] d) Lakshminarayanan, P. S.; Ravikumar, I.; Suresh, E.; Ghosh, P. Inorg. Chem. 2007, 46, 4769–4771.         [ Links ] e) Turner, D. R.; Paterson; M. J.; Steed, J. W. Chem. Commun. 2008, 1395–1397.         [ Links ] f) Arunachalam, M.; Ravikumar, I.; Ghosh, P. J. Org. Chem. 2008, 73, 9144–9147.         [ Links ] g) Heyer, D.; Lehn J.–M. Tetrahedron Lett. 1986, 27, 5869–5872.         [ Links ]

5. a)Mazik, M.; Sicking, W.; Boese, R. J. Org. Chem. 2004, 69, 7448–7462.         [ Links ] b) Mazik, M.; Radunz, W.; Sicking, W. Org. Lett. 2002, 4, 4579–4582.         [ Links ] c) Mazik, M. Chem. Soc. Rev. 2009, 38, 935–956.         [ Links ]

6. a) Ilioundis, C. A.; Tocher, D. A.; Steed, J. W. J. Am. Chem. Soc. 2004, 126, 12395–12402.         [ Links ] b) Okamoto, H.; Takemura, H.; Satake, K. Synthesis 2008, 39–44.         [ Links ]

7. a) Pecoraro, V. L.; Weitl, F. L.; Raymond K. N. J. Am. Chem. Soc. 1981, 103, 5133–5140.         [ Links ] b)Ebmeyer, F. Vögtle, F. Chem. Ber. 1989, 122, 1725–1727.         [ Links ] c) Grammenudi, S.; Vögtle, F. Angew. Chem. Int. Ed. Engl. 1986, 98, 1119–1121.         [ Links ] d) Lee, J. W.; Han, S. C., Kim J. H.; Lee, K. Bull. Korean Chem. Soc. 2006, 27, 1667–1670.         [ Links ]

8. Nativi, C.; Cacciarini, M.; Francesconi, O.; Vacca, A.; Moneti, G.; Lenco, A. Roelens, S. J. Am. Chem. Soc. 2007, 129, 477–4385.         [ Links ]

9. a) Usui, M.; Nishiwaki, T.; Anda, K.; Hida, M. Chem. Lett. 1984, 1561–1564.         [ Links ] b) Bottino, F.; Grazia, M. D.; Finocchiaro, P.; Fronczek, F. R.; Mamo, A.; Pappalardo, S. J. Org. Chem. 1988, 53, 3521–3529.         [ Links ]

10. a) Gibson, F. S.; Bergmeier S. C.; Rapoport, H. J. Org. Chem. 1994, 59, 3216–3218.         [ Links ] b) Várala, R.; Nuvula, S.; Adapa. S. R. J. Org. Chem. 2006, 71, 8283–8286.         [ Links ]

11. Dietrich, B.; Hosseini, M. W.; Lehn, J.–M.; Sessions, R. B. Helv. Chim. Acta 1985, 68, 289–299.         [ Links ]

12. Wallace, K. J.; Hanes, R.; Anslyn, E.; Morey, J.; Kilway, K. V.; Siegel, J. Synthesis 2005, 2080–2083.         [ Links ]

13. Feldman, A. K.; Colasson, B.; Fokin, V. V. Org. Lett. 2004, 6, 3897–3899.         [ Links ]

14. a) Zard, S. Z. Angew. Chem. Int. Ed. Engl. 1997, 36, 672–685.         [ Links ] b) Quiclet–Sire, B.; Zard, S. Z. Chem. Eur. J. 2006, 12, 6002–6016.         [ Links ] c) Degani, I.; Fochi, R. Synthesis, 1978, 365–368.         [ Links ]

15. Bernard, J.; Favier, A.; Zhang, L.; Nilasaroya, A.; Davis, T. P.; Barner–Kowollik, C.; Stenzel, M. H. Macromolecules 2005, 38, 5475–5484.         [ Links ]

16. a) García–Merinos, J. P.; Hernández–Pérez, J. P.; Martínez–García, L.; Rojas–Lima, S.; López–Ruiz, H. J. Mex. Chem. Soc. 2007, 51, 209–212.         [ Links ] b) Zard, Z. S. In: Radical Reactions in Organic Synthesis; Oxford Chemistry Masters: Oxford, 2003.         [ Links ] c) Renaud, P.; Sibi, M. P., in: Radicals in Organic Synthesis: Renaud, P., Sibi, M. P. Eds,: Wiley–VCH Weinheim, 2001. 2.         [ Links ]

17. Still, W. C.; Kahn, M.; Mitra, A.; J. Org. Chem. 1978, 43, 2923–2925.         [ Links ]

18. Rehse, K.; Luekens, U.; Claus, G.; Archiv der Pharmazie 1987, 320, 1233–1238.         [ Links ]

19. Wuytswinkel, G. V.; Verheyde, B.; Compernolle, F.; Toppet, S.; Dehaen, W. J. Chem. Soc, Perkin Trans. 1, 2000, 1337–1340.         [ Links ]

20. Grawe, T.; Schrader, T.; Zadmard, R.; Kraft, A. J. Org. Chem. 2002, 67, 3755–3763.         [ Links ]

21. Chiu, J. J.; Hart, H.; Ward, D. L. J. Org. Chem. 1993, 58, 964–966.         [ Links ]

22. a) Bruker Analytical X–ray Systems. SMART: Bruker Molecular Analysis Research Tool, Versions 5.057 and 5.618, 1997 and 2000.         [ Links ] b) Bruker Analytical X–ray Systems. SAINT + NT, Versions 6.01 and 6.04, 1999 and 2001.         [ Links ] c) Sheldrick, G. M. SHELX86, Program for Crystal Structure Solution; University of Göttingen: Germany, 1986.         [ Links ] d) Bruker Analytical X–ray Systems. SHELXTL–NT Versions 5.10 and 6.10, 1999 and 2000.         [ Links ]