What NMR Can Do for You
• Structure Elucidation of Small Molecules
• Structure identification of synthetic compounds, intermediates, impurities, mixtures, unknowns, regiochemistry, rotamerization
• Quantitative NMR • Chemical exchange: Equilibrium or A(Di)ssociation constants • Reaction monitoring or reaction rates • Diffusion coefficients (DOSY NMR): monomer? dimer? • Enantiomeric purity determination • Absolute stereochemistry determination • Dynamics (T1, T2 and NOE) • Intramolecular hydrogen-bond determination • Parahydrogen-NMR (enhance NMR signals thousands fold) to study
reaction pathways
• NMR Screening (Protein-Ligand Interaction)
• Structure and Dynamics of Macromolecules and
Complexes (e.g., peptides and proteins)
• Metabolites Analysis
NM
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by Lingyang Zhu
Count the Numbers
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13C-APT
1H Spectrum
Long-Range Connectivity: 1H-13C gHMBC Spectrum
11 18 1 6 24 21
28
8
29,13209 25
29,25
28,25
22,25
26,2526,29
22,21
19,21
23,21
4,2
10,2
4,64,18
7,67,11
8,68,11
7,9
22,20
20,2424,18
6,1120,18
21,18
24,20
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Relative Stereochemistry: 1D 1H-1H NOE Experiment
This problem can also be
readily solved by 1H-1H
J-coupling constants
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Regioisomer: 1H-19F NOE Experiment
NOE seen between 19F and proton at position 3, but not to the
pyrazole proton, suggesting the 5-position reaction, not 1-
position.
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3
3 6
NOE spectrum
1H spectrum
Regioisomer: 15N Chemical Shifts
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Based on the 15N chemical Shifts and
the connectivity from 1H-15N HMBC spectrum
Variable Temperature Experiments:
Tautomer Identification
HN
O
R
N11
12
13
14t
15t
16tN
O
R
HN
11
12
13
14
15
16
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HP
LC
D
ata
H
PLC
D
ata
5°C
25°C
qNMR: Determination of %TFA
by an Internal Standard
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qNMR: Determining [sample]
using NMR software
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M=(4 r3 N)/3
DOSY: Determination of MW
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MW=(4r3N)/3
D=kT/6r
Chemical Exchange in NMR:
Intra- and Inter-molecular process
Kassoc = kon/koff
k1
k-1
Keq determined by LW and Dd
kon
koff
+
Intra-
Inter-
STD Experiments
Meyer: 2003
U. Ottawa NMR Facility
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Collaborations & Publications Select Publications:
• A Metal-Free Electrocatalyst for Carbon Dioxide Reduction to Multi-Carbon Hydrocarbons and
Oxygenates. NatureComm 2016 (Kenis Group)
• Setting and Nanostructural Evolution of Metakaolin Geopolymers. JACERS 2016 (Struble
Group)
• Experimental evidence for a Co(I)/Co(III) redox process in olefin hydrogenation. JACS 2016
(Fout Group)
• Characterization of Sodium Mobility, Binding, and Apparent Viscosity in Full-Fat and Reduced-
Fat Model Emulsion Systems. JFMC 2016 (Schmidt Group)
• The interplay of Al and Mg speciation in advanced Mg battery electrolytes. JACS, 2015
(Gewirth Group)
• Control of protein orientation on gold nanoparticles. JPC, 2015 (Murphy group)
• Structure, bioactivity, and resistance mechanism of streptomonomicin, an unusual lasso peptide
from an understudied halophilic actnomycete. Chem Biol 2015 (Mitchell Group)
• Synthesis and Characterization of the Platinum-Substituted Keggin Anion α- H2SiPtW11O404-.
Inorg. Chem 2014 (Klemperer)
• Alkyne Mechanochemistry: Putative Activation by Transoidal Bending. RSC ChemComm. 2014
(Moore group)
• NMR structure of the S-linked glycopeptide sublancin 168. ACS Chem Biol. 2014 (van der
Donk group)
• New Reactions of Terminal Hydrides on a Diiron Dithiolate. JACS 2014 (Rauchfuss group)
NM
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Thank you
Please visit us at http://scs.illinois.edu/nmr/
Questions Always Welcome
HuiHui, Xixi and Lu