Scalar cross-relaxation detected in the NOESY spectra of oxazolidines and thiazolidines
Scalar cross-relaxation detected in the NOESY spectra of oxazolidines and thiazolidines
Anomalous cross-peaks observed in the NOESY spectra of 2,4-disubstituted thiazolidines and oxazolidines that cannot be attributed to classical dipolar NOE or chemical exchange peaks have been investigated experimentally and computationally and have been shown to arise from scalar cross-relaxation of the first kind. This process is stimulated by the relatively slow modulation of scalar couplings and, for the systems studied, arises from slow on–off proton exchange of the amino nitrogen, a process influenced by solution temperature, acidity, and concentration. The mechanism is likely to be significant for many systems in which proton exchange occurs on the millisecond time scale, and misinterpretation of these cross-peaks may lead to erroneous conclusions should their true origins not be recognized.
4142-4148
Panduwawala, Tharindi D.
fb150d6b-e61f-4769-8042-480f5428d6bf
Josa-Culleré, Laia
61cda35e-33bd-47c6-9470-1e6c8628f424
Kuprov, Ilya
bb07f28a-5038-4524-8146-e3fc8344c065
Odell, Barbara
b98ac430-5f30-4ff4-9b7f-9ae66ac9a2c2
Moloney, Mark G.
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Claridge, Timothy D.W.
c7583cca-a2f9-4ae2-8f78-66512a279f15
20 May 2016
Panduwawala, Tharindi D.
fb150d6b-e61f-4769-8042-480f5428d6bf
Josa-Culleré, Laia
61cda35e-33bd-47c6-9470-1e6c8628f424
Kuprov, Ilya
bb07f28a-5038-4524-8146-e3fc8344c065
Odell, Barbara
b98ac430-5f30-4ff4-9b7f-9ae66ac9a2c2
Moloney, Mark G.
ed22f0ed-d5eb-4aeb-9ac5-28b558b0576d
Claridge, Timothy D.W.
c7583cca-a2f9-4ae2-8f78-66512a279f15
Panduwawala, Tharindi D., Josa-Culleré, Laia, Kuprov, Ilya, Odell, Barbara, Moloney, Mark G. and Claridge, Timothy D.W.
(2016)
Scalar cross-relaxation detected in the NOESY spectra of oxazolidines and thiazolidines.
Journal of Organic Chemistry, 81 (10), .
(doi:10.1021/acs.joc.6b00458).
Abstract
Anomalous cross-peaks observed in the NOESY spectra of 2,4-disubstituted thiazolidines and oxazolidines that cannot be attributed to classical dipolar NOE or chemical exchange peaks have been investigated experimentally and computationally and have been shown to arise from scalar cross-relaxation of the first kind. This process is stimulated by the relatively slow modulation of scalar couplings and, for the systems studied, arises from slow on–off proton exchange of the amino nitrogen, a process influenced by solution temperature, acidity, and concentration. The mechanism is likely to be significant for many systems in which proton exchange occurs on the millisecond time scale, and misinterpretation of these cross-peaks may lead to erroneous conclusions should their true origins not be recognized.
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Accepted/In Press date: 2 March 2016
e-pub ahead of print date: 5 May 2016
Published date: 20 May 2016
Organisations:
Computational Systems Chemistry
Identifiers
Local EPrints ID: 401748
URI: http://eprints.soton.ac.uk/id/eprint/401748
ISSN: 0022-3263
PURE UUID: 7e347f27-ead2-4ae4-a352-13678682cb6b
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Date deposited: 20 Oct 2016 14:32
Last modified: 15 Mar 2024 03:43
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Contributors
Author:
Tharindi D. Panduwawala
Author:
Laia Josa-Culleré
Author:
Barbara Odell
Author:
Mark G. Moloney
Author:
Timothy D.W. Claridge
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