2D NMR PDF
2D NMR PDF
2D NMR PDF
Experiments
Chem 8361/4361:
Interpretation of Organic Spectra
3 90º
pulse
135º
2
pulse
1
2D NMR Spectroscopy
Who is Talking to Who?
1H–1H COSY (Correlation Spectroscopy)
– Tells you which protons are coupled to one another
– Very useful when peaks are overlapping in 1H NMR and you are
unable to calculate coupling constants, or when there are a lot of
similar coupling constants
– Cross peaks are coupled
to each other
H H
C C C
3H
1H 4H 3H
1H 2H 2H 1H 2H
Raffinose–a trisaccharide
2D NMR Spectroscopy
Who is Talking to Who?
1H–1H COSY (Correlation Spectroscopy)
Raffinose–a trisaccharide
2D NMR Spectroscopy
Who is Talking to Who?
1H–1H COSY (Correlation Spectroscopy)
2H
3H
3H
1H
2H
2H
1H
4H
1H
2D NMR Spectroscopy
Who is Talking to Who?
1H–1H COSY (Correlation Spectroscopy)
– DQF-COSY: Double Quantum Filtered COSY – cleans up the
spectrum by reducing noncoupled systems (e.g. CH3 singlets)
CH2
CH2
HO
H3C CH3
Ipsenol
2D NMR Spectroscopy
Who is Talking to Who?
1H–1H COSY (Correlation Spectroscopy)
– DQF-COSY: Double Quantum Filtered COSY – cleans up the
spectrum by reducing noncoupled systems (e.g. CH3 singlets)
CH2
CH2
HO
H3C CH3
Ipsenol
2D NMR Spectroscopy
Who is Talking to Who?
1H–1H COSY (Correlation Spectroscopy)
C6H10O2
2D NMR Spectroscopy
Who is Talking to Who?
1H–1H COSY (Correlation Spectroscopy)
O
Recall...
1H–1H COSY
H H
C C C
H
2H
H H 3H
C C C 3H
1H
H 2H
2H
4H
1H
2D NMR Spectroscopy
Who is Talking to Who?
1H–1H TOCSY (Total Correlation Spectroscopy)
– Tells you which protons are in the same spin system (a continuous chain
of spin-spin coupled protons)
– Magnetization from HA is transferred to HB, which then transfers to HC
and on down the line
HA HB HC HD HE
C C C C C
1D TOCSY H O H2
H O
O
HO HO OH
H OH OH
Spin System Identification H H H3
H5
H1 4.67 ppm
β-lactose
1D TOCSY
O O O O O O
4 3 H H
N3 6 1 N N O
5 O 2 O O
O O O
A B,C 2
D
Claridge, T. D. W. High-Resolution NMR Techniques in Organic Chemistry, 2nd Ed., Elsevier, 2009.
1D TOCSY
O
O
O
O D
O
HN
2
O
O
O B,C
O
HN
1 O
O 2
3
4
O A
O 5
6
N3
Claridge, T. D. W. High-Resolution NMR Techniques in Organic Chemistry, 2nd Ed., Elsevier, 2009.
2D TOCSY HO OH
Spin System Identification 3 4
O 1 6 N3
1H–1H TOCSY (Total Correlation Spectroscopy) 2 O 5
O
– Cross peaks are in the same spin system
COSY TOCSY
Claridge, T. D. W. High-Resolution NMR Techniques in Organic Chemistry, 2nd Ed., Elsevier, 2009.
2D TOCSY
– Cross peaks are in the same spin system
17
13
6
N 5 8
4
25
29 3 2 7
9 10
12 N 11
19
Intermediate in biomimetic 23
synthesis of manzamine
Claridge, T. D. W. High-Resolution NMR Techniques in Organic Chemistry, 2nd Ed., Elsevier, 2009.
2D TOCSY
– Cross peaks are in the same spin system
17
13
6
N 5 8
4
25
29 3 2 7
9 10
12 N 11
19
Intermediate in biomimetic 23
synthesis of manzamine
Claridge, T. D. W. High-Resolution NMR Techniques in Organic Chemistry, 2nd Ed., Elsevier, 2009.
2D TOCSY
– Cross peaks are in the same spin system
17
13
6
N 5 8
4
25
29 3 2 7
9 10
12 N 11
19
Intermediate in biomimetic 23
synthesis of manzamine
Claridge, T. D. W. High-Resolution NMR Techniques in Organic Chemistry, 2nd Ed., Elsevier, 2009.
New Developments
Deconvolution via MDEC
MDEC (Multi Frequency Homonuclear Decoupling)
– Conceptually the same as the homonuclear decoupling experiment
mentioned earlier, but allows multiple frequencies to be decoupled
at the same time
OH
1
2
3
7
(a) 1H NMR
(b) irr @ H-1
(c) irr @ H-1/H-7 H-2 (dddd)
(d) irr @ H-1/H-3a/H-7
J. Am. Chem. Soc. 2009, 131,
15994–15995
Me
New Developments Me H
Me H
X
H-2a
X
(a) 1H NMR
(b) 1D-TOCSY
irr @ H-3
(c) 1D-TOCSY
irr @ H-3 with
MDEC @ H-1b,
H-2b, H-3
C C C
C C C
Diastereotopic
Protons
C C C
H3C H CH3
H3C
O
H
H2C
Caryophyllene Oxide
2D NMR Spectroscopy
Who is Talking to Who?
HMQC
O
2D NMR Spectroscopy
Cl
HO
2D NMR Spectroscopy
Cl
HO
2D NMR Spectroscopy
Cl
HO
2D NMR Spectroscopy
Who is Talking to Who?
1H–13C COSY (Long Range)
H H H O
1 1 1
C C C H C O C H C C C H
2 3 2 3 2 3
C C C
H
1
C C C H
2 3
OH
OCH3
or
OCH3
OH
2D NMR Spectroscopy
Who is Talking to Who?
OH or OCH3
OCH3 OH
2D NMR Spectroscopy
Who is Talking to Who?
OH or OCH3
OCH3 OH
2D NMR Spectroscopy
Who is Talking to Who?
OH or OCH3
OCH3 OH
2D NMR Spectroscopy
Who is Talking to Who?
OH or OCH3
OCH3 OH
2D NMR Spectroscopy
Who is Talking to Who?
13C–13C COSY
C C C
CH3,CH3,CH2,CH3
OH
2D NMR Spectroscopy
2D NMR Spectroscopy
C C,CH
2D NMR Spectroscopy
Which
Isomer?
Br
O
2D NMR Spectroscopy
Br
O
2D NMR Spectroscopy
Br