Palladium-Catalyzed Amination in the Synthesis of Polyazamacrocycles Containing a 1,3-Disubstituted Benzene Moiety

Abstract

The synthesis of a new family of polyaza- and polyoxa­polyazamacrocycles by a simple and efficient one-pot palladium-catalyzed diamination of 1,3-dibromobenzene is described. The dependence of the nature of the starting polyamines on the yield of the products is demonstrated. The synthesis of N ^α ,N ^ω -bis(3-bromophenyl)-substituted polyamines is elaborated to obtain intermediates for the synthesis of polyazamacrocycles consisting of two polyamine and two benzene fragments (cyclodimers). The formation of tri- and tetraarylated polyamines is studied and regularities of the process are established. The synthesis of 1,3-bis(polyamino)-substituted benzenes is also described.

Key words

amines - aminations - haloarenes - homogenous catalysis - macrocycles

References

• 1 Bradshaw JS. Krakowiak KE. Izatt RM. Aza-Crown Macrocycles   Wiley & Sons; New York: 1993. 
• 2 Burguette MI. Escuder B. Garcia-Espana E. Luis SV. Miravet JF. Tetrahedron  2002,  58:  2839 
• 3 Militsopoulou M. Tsiakopoulos N. Chochos C. Magoulas G. Tetrahedron Lett.  2002,  43:  2593 
• 4 Favre-Reguillon A. Segat-Dioury F. Nait-Bouda L. Cosma C. Siaugue J.-M. Foos J. Guy A. Synlett  2000,  868 
• 5 Ray JK. Haldar MK. Gupta S. Kar GK. Tetrahedron  2000,  56:  909 
• 6 De Wall SL. Meadows ES. Barbour LJ. Gokel GW. Chem. Commun.  1999,  1553 
• 7 Meadows ES. De Wall SL. Barbour LJ. Gokel GW. Chem. Commun.  1999,  1555 
• 8 Kubo K. Yamamoto E. Sakurai T. Heterocycles  1998,  48:  2133 
• 9 Koulov AV. Mahoney JM. Smith BD. Org. Biomol. Chem.  2003,  1:  1467 
• 10 Vetrichelvan M. Lai Y.-H. Mok KF. Dalton Trans.  2003,  295 
• 11 Borisova NE. Reshetova MD. Ustynyuk YuA. Chem. Rev.  2007,  107:  46 
• 12 Witulski B. Weber M. Bergsträsser U. Desvergne J.-P. Bassani DM. Bouas-Laurent H. Org. Lett.  2001,  3:  1467 
• 13 Gouloumis A. Lawson RG. Vasquez P. Echegoyen L. Torres T. Tetrahedron  2002,  58:  961 
• 14 Gunnlaugsson T. Nieuwenhuyzen M. Richard L. Thoss V. J. Chem. Soc., Perkin Trans. 2  2002,  141 
• 15a Yang BH. Buchwald SL. J. Organomet. Chem.  1999,  576:  125 
• 15b Hartwig JF. Acc. Chem. Res.  1998,  31:  852 
• 16 Beletskaya IP. Bessmertnykh AG. Averin AD. Denat F. Guilard R. Eur. J. Org. Chem.  2005,  281 
• 17 Beletskaya IP. Averin AD. Pleshkova NA. Borisenko AA. Serebryakova MV. Denat F. Guilard R. Synlett  2005,  87 
• 18 Averin AD. Ulanovskaya OA. Borisenko AA. Serebryakova MV. Beletskaya IP. Tetrahedron Lett.  2006,  47:  2691 
• 19 Beletskaya IP. Averin AD. Ulanovskaya OA. Fedotenko IA. Borisenko AA. Serebryakova MV. Denat F. Guilard R. Chem. Lett.  2005,  34:  1100 
• 20 Averin AD. Ulanovskaya OA. Fedotenko IA. Borisenko AA. Serebryakova MV. Beletskaya IP. Helv. Chim. Acta  2005,  88:  1983 
• 21 Beletskaya IP. Averin AD. Borisenko AA. Denat F. Guilard R. Tetrahedron Lett.  2003,  44:  1433 
• 22 Wolfe JP. Buchwald SL. J. Org. Chem.  2000,  65:  1144 
• 23 Wolfe JP. Tomori H. Sadighi JP. Yin J. Buchwald SL. J. Org. Chem.  2000,  65:  1158 
• 24 Beletskaya IP. Bessmertnykh AG. Averin AD. Denat F. Guilard R. Eur. J. Org. Chem.  2005,  261 
• 25 Ukai T. Kawazura H. Ishii Y. Bonnet JJ. Ibers JA. J. Organomet. Chem.  1974,  65:  253