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Issue 2, 2013
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Chiral thiouronium salts: synthesis, characterisation and application in NMR enantio-discrimination of chiral oxoanions

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Abstract

Chiral thioureas and functionalised chiral thiouronium salts were synthesised starting from the relatively cheap and easily available chiral amines: (S)-methylbenzylamine and rosin-derived (+)-dehydroabietylamine. The introduction of a delocalised positive charge to the thiourea functionality, by an alkylation reaction at the sulfur atom, enables dynamic rotameric processes: hindered rotations about the delocalised CN and CS bonds. Hence, four different rotamers/isomers may be recognised: synsyn, synanti, antisyn and antianti. Extensive 1H and 13C NMR studies have shown that in hydrogen-bond acceptor solvents, such as perdeuteriated dimethyl sulfoxide, the synsyn conformation is preferable. On the other hand, when using non-polar solvents, such as CDCl3, the mixture of synsyn and synanti isomers is detectable, with an excess of the latter. Apart from this, in the case of S-butyl-N,N′-bis(dehydroabietyl)thiouronium ethanoate in CDCl3, the 1H NMR spectrum revealed that strong bifurcated hydrogen bonding between the anion and the cation causes global rigidity without signs of hindered rotamerism observable on the NMR time scale. This suggested that these new salts might be used as NMR discriminating agents for chiral oxoanions, and are indeed more effective than their archetypal guanidinium analogues or the neutral thioureas. The best results in recognition of a model substrate, mandelate, were obtained with S-butyl-N,N′-bis(dehydroabietyl)thiouronium bistriflamide. It was confirmed that the chiral recognition occurred not only for carboxylates but also for sulfonates and phosphonates. Further 1H NMR studies confirmed a 1 : 1 recognition mode between the chiral agent (host) and the substrate (guest); binding constants were determined by 1H NMR titrations in solutions of DMSO-d6 in CDCl3. It was also found that the anion of the thiouronium salt had a significant influence on the recognition process: anions with poor hydrogen-bond acceptor abilities led to the best discrimination. The presence of host–guest hydrogen bonding was confirmed in the X-ray crystal structure of S-butyl-N,N′-bis(dehydroabietyl)thiouronium bromide and by computational studies (density functional theory).

Graphical abstract: Chiral thiouronium salts: synthesis, characterisation and application in NMR enantio-discrimination of chiral oxoanions

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Article information


Submitted
16 Oct 2012
Accepted
14 Nov 2012
First published
15 Nov 2012

This article is Open Access

New J. Chem., 2013,37, 515-533
Article type
Paper

Chiral thiouronium salts: synthesis, characterisation and application in NMR enantio-discrimination of chiral oxoanions

M. B. Foreiter, H. Q. N. Gunaratne, P. Nockemann, K. R. Seddon, P. J. Stevenson and D. F. Wassell, New J. Chem., 2013, 37, 515
DOI: 10.1039/C2NJ40632B

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