An examination of factors influencing small proton chemical shift differences in nitrogen-substituted monodeuterated methyl groups
File(s)
Published version
Author(s)
Elliott, Stuart J
Ogba, O Maduka
Brown, Lynda J
O'Leary, Daniel J
Type
Journal Article
Abstract
Monodeuterated methyl groups have previously been demonstrated to provide access to
long-lived nuclear spin states. This is possible when the CH2D rotamers have sufficiently different
populations and the local environment is chiral, which foments a non-negligible isotropic chemical
shift difference between the two CH2D protons. In this article, the focus is on the N-CH2D group of
N-CH2D-2-methylpiperidine and other suitable CH2D-piperidine derivatives. We used a combined
experimental and computational approach to investigate how rotameric symmetry breaking leads to
a
1H CH2D chemical shift difference that can subsequently be tuned by a variety of factors such as
temperature, acidity and 2-substituted molecular groups.
long-lived nuclear spin states. This is possible when the CH2D rotamers have sufficiently different
populations and the local environment is chiral, which foments a non-negligible isotropic chemical
shift difference between the two CH2D protons. In this article, the focus is on the N-CH2D group of
N-CH2D-2-methylpiperidine and other suitable CH2D-piperidine derivatives. We used a combined
experimental and computational approach to investigate how rotameric symmetry breaking leads to
a
1H CH2D chemical shift difference that can subsequently be tuned by a variety of factors such as
temperature, acidity and 2-substituted molecular groups.
Date Issued
2021-09-01
Date Acceptance
2021-08-26
Citation
Symmetry, 2021, 13 (9)
ISSN
2073-8994
Publisher
MDPI AG
Journal / Book Title
Symmetry
Volume
13
Issue
9
Copyright Statement
© 2021 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ 4.0/).
License URL
Identifier
10.3390/sym13091610
Subjects
CENTER-DOT-O
CH2D
chemical shift difference
diastereotopicity
equilibrium isotope effects
LONG-LIVED STATES
MAGNETIZATION
monodeuterated methyl group
Multidisciplinary Sciences
NMR
NUCLEAR-SPIN STATES
O HYDROGEN-BOND
Science & Technology
Science & Technology - Other Topics
SINGLET-ORDER
Publication Status
Published
Article Number
1610
Date Publish Online
2021-09-02