Chemical Shift
Peak Intensity
Spin-spin Coupling
Sample Preparation: Deuterated Solvents
Spin-spin Coupling
12
10
5.5
5
4.5
3.5
4
3
2.5
02
0
45
90
135
180
Spin-spin Coupling
1.
2.
2 = (Jexp-Jcalc)2
Spin-spin Coupling
Spin-spin Coupling
Multiplet Appearance
8=8
20
6=6
16
5=5
14
4=4
3=3
10
2=2
1=1
0=0
J14 = J12
J14 = J14'
Spin-spin Coupling
Me
H
Me
Me
H
OH
OH
OPMB
Spin-spin Coupling
Spin-spin Coupling
from 1 to 2n (arbitrarily) from left to right by analogy to the examples shown below.
a) ddd
1 2 3 4
b) ddd
5 6 7 8
c) dddd
1
2
3
45
9 1213 14
10
11
15
16
Spin-spin Coupling
2. Systematically identify the J's by the following series of steps. Adopt the
{1 to 2} is J1
ii)
{1 to 3} is J2
iii)
iv)
v)
remove from further consideration the components corresponding to the remaining combinations
of the first three J values [i.e., (J1 + J3), (J2 + J3), and (J1 + J2 + J3)
vi)
Spin-spin Coupling
J2
J1
2
3
4 5
6
7
8
9
10
11
12 13
14
15
16
Spin-spin Coupling
J1
J2
J1
2
3
4 5
6
7
8
9
10
11
12 13
14
15
16
Spin-spin Coupling
2. Systematically identify the J's by the following series of steps. Adopt the
{1 to 2} is J1
ii)
{1 to 3} is J2
iii)
iv)
v)
remove from further consideration the components corresponding to the remaining combinations
of the first three J values [i.e., (J1 + J3), (J2 + J3), and (J1 + J2 + J3)
vi)
Spin-spin Coupling
J4
v)
J3
J2
v)
J3
J2
v)
J3
J1
iv)
J3
iii)
J2
J2
ii)
i)
J1
J1
J1
2
3
4 5
6
7
8
9
10
11
12 13
14
15
16
Spin-spin Coupling
H
H
Ha
Me
O
Me H
Hb
PMB
Ha
Me
3
2
J1 J2 J5
J3 J6
J4
PMB
Me H
Hb
dddddd
Spin-spin Coupling
Ha
Me
O
Me H
Hb
dddddd
PMB
Spin-spin Coupling
Spin-spin Coupling
H D
N
NH
S
Me
Me
Me
NH
O
OH
O
Spiruchostatin A
1. Masuoka, Y.; Nagai, A.; Shin-ya, K.; Furihata, K.; Nagai, K.; Suzuki, K.; Hayakawa, Y.;
Seto, H. "Spiruchostatins A and B, novel gene expression-enhancing substances produced by
Pseudomonas sp.," Tetrahedron Lett. 2001, 42, 41-44.
Spin-spin Coupling
Spin-spin Coupling
N
H
H
Me
N
H
O
2''
OH
H
O
H
i-Bu
H
H
H
OH
H O
H
H
O
4''
3'
7'''
3'
2'''
6'''
2'''
2''
OH
7'''
6''
60 C
25 C
3.5
3.3
3.1
2.9
2.7
2.5
2.3
Spin-spin Coupling
J1
J2
Et
S
Me
NH
O
J4
67, 4014-4016.
NH
S
J3
H
N
Me
3'''
O
OH
O
J5
60 C
5.53
5.52
5.51
5.5
5.49
5.48
5.47
Spin-spin Coupling
3'-H
(dd 3.9, 15.0)
3.154
3.134
3.114
3.094
3.074
3.054
5.63
5.62
5.61
5.6
S 7''' H
H
H
6''' H
4'''H
H
i-Bu
OH
H
H
6'''-H
(dddd 2.4, 9.6, 12.0, 15.0)
5.64
3.034
4'''-H
(ddd 2.1, 2.1, 15.4)
5.65
H
3' H
N
3.174
Me
H
H O
5.59
5.58
2.52
2.5
2.48
2.46
2.44
Spin-spin Coupling
N
H
H
Me
N
H
O
OH
2'' a
17 % C6D6
60 C
H O
H
H
H
S 7''' H
H
i-Pr
OH
H
H
H
6''' H
O
245
7''' (dddd
3.0, 3.0, 9.2, 13.1)
195
145
2'' b
7'''
6''' (dddd
3.2, 5.5, 6.5, 13.1)
95
6'''
45
-5
2.7
2.65
2.6
2.55
2.5
0 % C6D6
2.8
2.75
2.7
2.65
2.6
2.6
2.58
2.56
2.54
2.52
2.5