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 methylen

Applications of dynamic combinatorial chemistry for the determination of effective molarity / Ciaccia, Maria; Irene, Tosi; Laura, Baldini; Roberta, Cacciapaglia; Mandolini, Luigi; DI STEFANO, Stefano; Christopher A., Hunter. - In: CHEMICAL SCIENCE. - ISSN 2041-6520. - STAMPA. - 6:(2015), pp. 144-151. [10.1039/C4SC02347A]

Applications of dynamic combinatorial chemistry for the determination of effective molarity

CIACCIA, MARIA;MANDOLINI, Luigi;DI STEFANO, Stefano
;
2015

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 methylen
2015
molecular recognition; systems chemistry; thermodynamic control; induced amplification; formaldehyde acetals; covalent chemistry; imine metathesis; libraries; macrocyclization; cooperativity
01 Pubblicazione su rivista::01a Articolo in rivista
Applications of dynamic combinatorial chemistry for the determination of effective molarity / Ciaccia, Maria; Irene, Tosi; Laura, Baldini; Roberta, Cacciapaglia; Mandolini, Luigi; DI STEFANO, Stefano; Christopher A., Hunter. - In: CHEMICAL SCIENCE. - ISSN 2041-6520. - STAMPA. - 6:(2015), pp. 144-151. [10.1039/C4SC02347A]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/655212
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