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. 2020 Apr 3;85(7):5058-5064.
doi: 10.1021/acs.joc.9b03082. Epub 2020 Mar 13.

Selective Carboxylate Recognition Using Urea-Functionalized Unclosed Cryptands: Mild Synthesis and Complexation Studies

Patryk Niedbała  1 , Maciej Majdecki  1 , Kajetan Dąbrowa  1 , Janusz Jurczak  1
Affiliations

Selective Carboxylate Recognition Using Urea-Functionalized Unclosed Cryptands: Mild Synthesis and Complexation Studies

Patryk Niedbała et al. J Org Chem. .

Abstract

Herein we present the synthesis and evaluation of anion-binding properties of 12 new receptors from the unclosed cryptand family. Their core is built on the stable 26-membered tetraamidic macrocyclic scaffold, whereas various alkyl and aryl urea substituents were introduced after a yield-limiting macrocyclization step (65-98%). The receptors strongly bind anions, in particular carboxylates, even in a highly competitive solvent mixture (DMSO-d6 + H2O 95:5 v/v).

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Synthesis of N-Boc-Protected Macrocyclic Precursor 3 and Its Postfunctionalization to 4a–l
Scheme 2
Scheme 2. Energy-Minimized Structures of Free Receptor 4c and Its Complex with the Benzoate Anion
Scheme 3
Scheme 3. Carboxylate-Induced Deprotonation of the Receptor 4g and Corresponding Charge-Transfer Transition States
Figure 1
Figure 1
Structures of receptors 4d and 5.
Figure 2
Figure 2
Crystal structure of receptor 4l, top (a) and side (b) views. Nonacidic protons and remaining disordered water molecules were omitted for clarity.
See this image and copyright information in PMC

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