Anion and carboxylic acid binding to monotopic and ditopic amidopyridine macrocycles

Ivan V. Korendovych, Mimi Cho, Olga V. Makhlynets, Phillip L. Butler, Richard J. Staples, Elena V. Rybak-Akimova

Research output: Contribution to journalArticle

36 Scopus citations

Abstract

(Graph Presented) Binding of inorganic anions, carboxylic acids, and tetraalkylammonium carboxylates by macrocyclic compounds of different size was studied by NMR in DMSO-d6. It has been shown that at least a 15-membered ring is necessary for successful recognition of fluoride. Larger macrocycles were shown to bind HSO4-, H2PO 4-, Cl-, and carboxylic acid salts. Effects of binding topicity are discussed. The 30-membered macrocycles 4 and 4m selectively bind substrates that are size- and shape-complementary: maximum binding is observed for dicarboxylic acids and dicarboxylates with four-carbon chains, and the binding constant for association of fumaric acid and 4 is ca. 5 orders of magnitude higher than that of maleic acid. The 30-membered macrocycle 4m showed selectivity toward α-ketocarboxylic acids. Secondary amino groups were not crucial for binding of fluoride to the macrocycles; however, they proved to be very important for selectivity and strength of carboxylic acid binding. The X-ray structure of the adduct of 4 and nitrobenzoic acid confirmed the guest H-bonding with both the amide and the secondary amino groups of the 30-membered macrocyclic host.

Original languageEnglish (US)
Pages (from-to)4771-4782
Number of pages12
JournalJournal of Organic Chemistry
Volume73
Issue number13
DOIs
StatePublished - Jul 4 2008

ASJC Scopus subject areas

  • Organic Chemistry

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