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Issue 1, 2015
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Applications of dynamic combinatorial chemistry for the determination of effective molarity

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Abstract

A new strategy for determining thermodynamic effective molarities (EM) for macrocylisation reactions using dynamic combinatorial chemistry under dilute conditions is presented. At low concentrations, below the critical value, Dynamic Libraries (DLs) of bifunctional building blocks contain only cyclic species, so it is not possible to quantify the equilibria between linear and cyclic species. However, addition of a monofunctional chain stopper can be used to promote the formation of linear oligomers allowing measurement of EM for all cyclic species present in the DL. The effectiveness of this approach was demonstrated for DLs generated from mixtures of 1,3-diimine calix[4]arenes, linear diaminoalkanes and monoaminoalkanes. For macrocycles deriving from one bifunctional calixarene and one diamine, there is an alternating pattern of EM values with the number of methylene units in the diamine: odd numbers give significantly higher EMs than even numbers. For odd numbers of methylene units, the alkyl chain can adopt an extended all anti conformation, whereas for even numbers of methylene units, gauche conformations are required for cyclisation, and the associated strain reduces EM. The value of EM for the five-carbon linker indicates that this macrocycle is a strainless ring.

Graphical abstract: Applications of dynamic combinatorial chemistry for the determination of effective molarity

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Publication details

The article was received on 04 Aug 2014, accepted on 16 Sep 2014 and first published on 29 Sep 2014


Article type: Edge Article
DOI: 10.1039/C4SC02347A
Citation: Chem. Sci., 2015,6, 144-151
  • Open access: Creative Commons BY license
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    Applications of dynamic combinatorial chemistry for the determination of effective molarity

    M. Ciaccia, I. Tosi, L. Baldini, R. Cacciapaglia, L. Mandolini, S. Di Stefano and C. A. Hunter, Chem. Sci., 2015, 6, 144
    DOI: 10.1039/C4SC02347A

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