Martin, Benjamin, Knochel, Paul, Heinz, Benjamin, Djukanovic, Dimitrije, Siemens, Fiona and Idriess, Mohamed (2021) Regioselective Amination or Alkoxylation of Halogenated Amino-, Thio- or Alkoxypyridines via Pyridyne Intermediates. Synthesis, 53. A-I.

Abstract

The treatment of 3-halopyridines (Cl, Br) bearing an R-substituent in position 2 (R = OEt, NEt2, N-piperidyl, or SEt) or in position 5 (R = OMe, OEt, SEt, NMe2, NEt2, or aryl) with KHMDS and an amine at 25 °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 °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:	Article
Keywords:	potassium bases, pyridines, amination, alkoxylation, pyridynes
Date Deposited:	01 Feb 2022 00:45
Last Modified:	01 Feb 2022 00:45
URI:	https://oak.novartis.com/id/eprint/45742