Tutorial on 2D-NMR:

Using COSY & HSQC to

Assist in Assigning 1H &
13C NMR Spectra

H NMR

Chemical shift () depends on

molecular structure and solvent
1H nuclei sensitive to hybridization of
atom to which H is attached and
electronic effects
EDGs shield nuclei shift upfield lower
EWGs deshield nuclei shift downfield
higher
Downfield
Deshielded

Upfield
Shielded

10 ppm

0 ppm

H NMR

Spin-spin coupling effects: interaction

between nuclei through bonds
Causes splitting in observed peak (s, d, dd, t,
m)
Coupling constants: magnitude of splitting
(Hz)
Hz (not ppm) since effect is independent of
applied mag. fld.
Caused by mag. fld. of another nuclei

2-D NMR
Determine structure (especially for
molecules too complicated for 1-D
NMR)
Involves series of 1-D NMR
experiments
Doesnt need to use the complicated
coupling constants

Correlation Spectroscopy
(COSY)
Homonuclear: plots 1H NMR on both x and y-axis
Diagonal divides the spectrum into 2 equal halves
Cross-signals: symmetrical to diagonal; contain
the relevant info
FAB-FOUR
1H NMR (~5 min)
COSY (~30 min)
13C NMR (depends)
HSQC (~30 min)

H4

H3

H2

H4
H2

H3

H8

H4 H
7

H3

H6 H2

H4 H7

3
7
4

H8
H6 H2

H3

8
6

H6 H2

H8

H4 H
7

H3

H1

H4 H7

3
7

H8

4
8

H6 H2
H1

H3

H6 H2

H8

H4 H
7

H3

H5H1

H4 H7

3
7

H8

4
8

H6 H2
H5H1

H3

H9

H6 H2

H
H8 10

H4 H
7

H3

H5H1 H11

H4 H7

3
7

H10
H8

H9
H6 H2

810

H11
H5H1

H3

11
5

H9

H6 H2

H
H8 10

H4 H
7

H3

H5H1 H11

H4 H7

3
7

H10
H8

H9
H6 H2

810

H11
H5H1

H3

11
5

LONG-RANGE COUPLING
H9

H6 H2

H
H8 10

H4 H
7

H3

H5H1 H11

H4 H7

3
7

H10
H8

H9
H6 H2

810

H11
H5H1

H3

11
5

Heteronuclear Single Quantum

Coherence (HSQC)
Plots 1H NMR on x-axis and 13C NMR
on y-axis
Utilizes 1 bond coupling between H
and C
Eliminating all the H containing Cs
eliminates many Cs assignments
Leaves only on-H containing Cs to assign

HSQC Spectrum

H5H1 H11

H9

H6 H2

H
H8 10

H4 H
7

H3

51
10

11
6

H5H1 H11

H9

H6 H2

H
H8 10

H4 H
7

H3

51
10

11
6

# of total peaks:

# of non-H C peaks: 2

??????????
C12, C13
C1514,, C15
14,, C
17, C17

C9 C8
C4
C13
C12

C6
C2

C11

C7
C1
C3
C10 C5

Thank You
Any Questions?