B.

Through chiroptical methods

- qualitative: optical activity
(refraction phenomenon, circularly polarized light)
gives , which gives []
- quantitative
I. ORD (optical rotatory dispersion)
2. Relative configuration continued
- measures the specific rotation as a function of the wavelength
- in the UV-Vis region, 200-800 nm
[ ] [ ]
T T
M


100
=
M: molar mass
- instead of the specific rotation [], often the molrotation [] is used
Molrotation: rotation on a per mole basis,
for the comparison of [] for different compounds.
[]
, nm
- ORD spectrum for a transparent compound
(compound does not absorb in that spectral region)
2. Relative configuration continued
- plain (dispersion) curve
- monotonic change
- +: rises towards shorter
-: falls towards shorter
[]
,nm
positive curve
negative curve
300 700
200
200
100
100
OH
H
OH
H
- ORD spectrum for an absorbing compound
- Cotton-effect (CE) curve
- anomalous change
- cross-over point
[]
,nm
700
3320
3320
3080
3080 positive curve, positive CE
negative curve, negative CE
294
UV-Vis signal inserted for clarification
plain dispersion
O
- two more issues on ORD spectra
2. Relative configuration continued
O
O
H
O
O
H
O
- negative plain dispersion + positive CE
[]
,nm
I
II
Djerassi, Optical rotatory dispersion, McGraw-Hill, NY, 1960
skeleton of II causes the
negative background curve
- importance of second cross-over point
700
[]
,nm
500
O
S
S
Ph
3
C
cross-over close to the
Na D-line
O
H
COOH
I
O
H
COOH
I
O
H
COOH
I
- two more issues on ORD spectra
2. Relative configuration continued
, nm
Djerassi, Optical rotatory dispersion, McGraw-Hill, NY, 1960
- importance of second cross-over point: example
[]
10
-2
I II
[]
D
I
II
III
III
(-) (+) (+)
[]
D
but all plain dispersion curves positive!
-magnitude of is normalized as specific ellipticity []:
- instead of the specific ellipticity [], often the molar ellipticity [] is used
B. Through chiroptical methods
II. CD (circular dichroism) spectroscopy
2. Relative configuration continued
- measures the absorption as a function of the wavelength
- in the UV-Vis region, 200-800 nm
[ ] [ ]
T T
M

=
100
- but: anisotropic absorption of circularly polarized light
=
L
-
R
(by definition)
leads to elliptically polarized light, which has an ellipticity

, nm
?
[ ] cl
T

=
Insert
Polarized light
http://www.enzim.hu/~szia/cddemo/edemo0.htm
This is what happens to circularly polarized light in an absorbing sample:
back
Insert
Polarized light
http://www.enzim.hu/~szia/cddemo/edemo0.htm
This is how circular dichroism comes about (formation of elliptically polarized light):
Here the right circularly polarized wave is absorbed to a greater extent.
B. Through chiroptical methods
II. CD (circular dichroism) spectroscopy
2. Relative configuration continued
- the sign of defines the sign of the CD
- the sign of the CD is the same as that of the ORD at the CE
[]
,nm
positive CE
negative CE
- CD spectrum (for an absorbing compound)
UV-Vis signal inserted for clarification
- Cotton-effect (CE) curve
O
[]
or
- two more issues on CD/ORD spectra
2. Relative configuration continued
- CD maximum coincides with ORD cross-over
superposition of both spectra (not normally done):
700
[]
,nm
[]
or
O
O
H
,nm
300 700
- there might not be a CD spectrum, but there will always be an ORD!
[]
- and one more issue on CD/ORD spectra
2. Relative configuration continued
- multiple CEs (here three)
in the CD are easy
to interpret
in the ORD are near
impossible to interpret
- and the final issue on CD spectra
2. Relative configuration continued
- sensitivity in comparison to UV-Vis spectra
very sensitive to
stereochemical issues
very insensitive
O
O
tBu
tBu
3 diastereomers:
O
O
tBu
tBu
O
O
tBu
tBu
O
O
tBu
tBu