TWO – Dimensional NMR

The two-dimensional homonuclear (H, H)-corelated NMR experiment

yields NMR spectra in which 1H chemical shifts along both frequency
axes correlated with each other. This technique has become known as
COSY (correlated Spectroscopy).
H,H-COSY (Homonuclear correlation spectroscopy) of Ethyl acetate
 COSY - COrrelation SpectroscopY
(correlates scalarly coupled protons)

The gradient DQF-COSY sequence: H3 H4H4 H1 H1 H3 H2 H2

H2
1H
d1 t1 H2

Grad. H3

H1
H1

H H H H H4
1 3 1 3
X X X H4
X O R1
R2 X X X X

H H O H H
2 4 2 4 H3
H,H-COSY of b-Ionone
 DQF-COSY of Taxol
(expansion #2)
Known from TOCSY:
F1
6.91, 5.72, 4.72 3.48 (ppm)

4.0
Known from 15N-HSQC: 6.91 is NH
4.5
Known from 13C-HSQC: 3.48 is OH
5.0

X
4.72 5.5

H
55.04 X 6.0

6.91 73.20
HN H 6.5

5.72 OH
3.48
7.0

X O 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5

F2 (ppm)
NOESY (Nuclear Overhauser and Exchange Spectroscopy) of
b-Ionone
H,C-COSY Spectrum of Aphanamol
HMQC (1H-detected-heteronuclear multiple-quantum coherence)
Spectrum of Strychnine
HSQC - Heteronuclear Single Quantum Coherence
 Results from the HSQC experiment:
Quaternery
Proton-Carbon Pairs
Carbons
8.06 (2) 130.21 (d*) 4.72 (1) 73.20 (d) 203.61 (s)
7.67 (2) 127.04 (d*) 4.33 (1) 72.18 (d) 172.72 (s)
7.54 (1) 133.71 (d) 4.23 (1); 4.13 (1) 76.52 (t) 171.22 (s)
7.44 (2) 128.70 (d*) 3.73 (1) 45.64 (d) 170.35 (s)
7.42 (1) 131.97 (d) 3.48 (1) 167.04 (s)
7.41 (2) 127.04 (d*) 2.47 (1); 1.81 (1) 35.63 (t) 167.01 (s)
7.35 (2) 129.03 (d*) 2.38 (1) 141.95 (s)
7.33 (2) 128.72 (d*) 2.31 (3) 22.63 (q) 137.99 (s)
7.28 (1) 128.37 (d) 2.29 (1); 2.22 (1) 35.72 (t) 133.65 (s)
6.91 (1) 2.17 (3) 20.84 (q) 133.23 (s)
6.21 (1) 75.57 (d) 1.73 (1) 129.18 (s)
6.16 (1) 72.41 (d) 1.72 (3) 14.83 (q) 81.19 (s)
5.72 (1) 55.04 (d) 1.62 (3) 9.57 (q) 79.05 (s)
5.61 (1) 74.98 (d) 1.17 (3) 26.88 (q) 58.65 (s)
4.87 (1) 84.41 (d) 1.08 (3) 21.83 (q) 43.19 (s)

Conclusions: We have:
a, cross-peaks identify C-H pairs 15 quaternary
b, no cross-peak at a 1H chemical shift: exchangable proton 17 + 6* CH
c, no cross-peak at a 13C chemical shift: quaternary carbon 3 CH2
6 CH3 carbons
Long-range H,C-COSY Spectrum of b-Ionone
HMBC (1H-multilicity bond connectivity) of Strychnine
 H
H

COOCH 3
16
OH
H H
3
HO
COOCH 3

NOE COOCH 3
H H
25 26
12 18
24

HO 16
OH
COOCH 3
23
 2 O
1
3
OCH3

4 6