Palladium-Catalyzed Amination of 3,5-Dihalopyridines – a Convenient Route to New Polyazamacrocycles

✍ Scribed by Alexei D. Averin; Olesya A. Ulanovskaya; Ilya A. Fedotenko; Anatolii A. Borisenko; Marina V. Serebryakova; Irina P. Beletskaya

• Publisher: John Wiley and Sons
• Year: 2005
• Tongue: German
• Weight: 302 KB
• Volume: 88
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/hlca.200590152

✦ Synopsis

Abstract

Pd‐Catalyzed amination of 3,5‐dibromo‐ and 3,5‐dichloropyridine (1a and 1b, resp.) with linear polyamines 2 leads to the formation of a new family of pyridine‐containing macrocycles 3 with an ‘exo’‐oriented pyridine N‐atom (Schemes 1 and 2). The dependence of the macrocycle yield on the nature of the halogen atom, the length of the polyamine chain and C/N atom ratio, and the composition of the catalytic system is studied. The synthesis of mono‐ and bis(5‐halopyridin‐3‐yl)‐substituted polyamines 4, 5, 8, 9, and of 3,5‐bis(polyamino)‐substituted pyridines 6 is described (Schemes 3 and 4), and the use of these compounds as intermediates on the way to the macrocycles 7, 16, and 18 with larger cavity (‘cyclodimers’ and ‘cyclotrimers’) is demonstrated (Schemes 5–10).