Regioselective Amination or Alkoxylation of Halogenated Amino-, Thio- or Alkoxypyridines via Pyridyne Intermediates

Heinz, Benjamin; Djukanovic, Dimitrije; Siemens, Fiona; Idriess, Mohamed; Martin, Benjamin and Knochel, Paul (2022): Regioselective Amination or Alkoxylation of Halogenated Amino-, Thio- or Alkoxypyridines via Pyridyne Intermediates. In: Synthesis, Vol. 54, No. 22: pp. 5055-5063

Abstract

The treatment of 3-halopyridines (Cl, Br) bearing an R-substituent in position 2 (R = OEt, NEt (2) , N -piperidyl, or SEt) or in position 5 (R = OMe, OEt, SEt, NMe (2) , NEt (2) , or aryl) with KHMDS and an amine at 25 degrees C for 12 hours in THF provided regioselectively 3- and 4-aminated pyridines in 56-90% yields. The reaction of 3-bromo-2-diethylaminopyridine with various alcohols in the presence of t -BuOK/18-crown-6 in THF at 80 degrees C for 20-60 hours gave various 4-alkoxy-2-diethylaminopyridines in 61-81% yields. These substitution reactions were proposed to proceed via pyridyne intermediates.

• Item Type: Journal article
• Faculties: Chemistry and Pharmacy > Department of Chemistry
• Subjects: 500 Science > 540 Chemistry
• ISSN: 0039-7881
• Language: English