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2 Stereochemistry
Structural representations that convey 3-D information
CH3 Cl H CH2CH3
CH3
Cl
H CH2CH3
Cl H
CH3 CH2CH3
Cl
CH3
CH2CH3
Fischer projection.
CH3 CH3 H Cl H3C H H H Cl
H H H3C
H Cl
O Ph Ph N H
Sawhorse representation.
AcO O O HO H H H AcO OCPh O O OH
Newman projection
Taxol
Isomerism
Isomers Different compounds that have the same molecular formula.
Conformational IsomerStereoisomers that are superimposable by rotation around a single bond. Enantiomer Isomers that are non-superimposable mirror images to each other.chiral DiastereomerIsomers that are non-superimposable, not mirror images. Cis-trans isomer ( geometric isomer ) configurational isomers differ around a double bond or cyclic structure.
H3C H
CH 3 H
CH 3 H
C2, v, v
CH 3
C2, h
H F1 D1 H
Cl2 D2 F2 i F2 D2
H2
Cl1 D1 F1
Cl1
H1
C2hi S2
Y Ci
X Cs X
X C2
X X
X C2v X C2h X X
X X D2h X
X X X D2d
ChiralityMolecules that are not superimposable with their mirror image chiral. (enantiomeric ) dissymmetric molecules molecules without Sn axis (including n=1). Dissymmetric molecules are chiral, chiral molecules are dissymmetric. Dissymmetrical with a chiral center (asymmetric): asymmetric moleculesmolecules without any symmetry element, except C1.
CH2CH3 Br O F Cl CH3 Ph S H3CH2CH2C H3C P
CO2H
2 3
N Nu CH3 R3
HO2C
H Br
CO2H
C2
O O O H O
C6
H H H
C3
D2
D2
D3
axis of chirality
C1
H
NH2
axis of chirality
chiral
axis of chirality
NO2 HO2C
* * *
CO2H
Non-dissymmetric moleculeshaving Ci, Cs, Cnv, Cnh, Dnh, H3C H Dnd, Td, Oh or Sn symmetry.
H H H3C N H CH3 CH3
( S1, S2i )
H3C N CH3
CH3
achiral
C H
>
CH
NH
>
>
CH
CH 2 >
CH 2
CH 3
H3C CH H3C
HO HC
OCH3 CH CH2CH3
Cl
(S)
C
CH3
Cl
H2C C
CH2 HC HC OH
CH3
H2C HC HC OH
H CH2
C
H
(S)
H2C
CH2
3
CH3 H
CH3 H
2
ClH2C
(R)
1
CHCl2 BrH2C
(S)
1 2
CHCl2
CH3 HO
4' 8'
H3C CH3
CH3 CH3
CH3
H CH3
CH2OH H
H CH3
CH3 17 13
20 C H
OH
1 2
H3CH2CH2C H3C P
OH
(S)
3
Chirality about an axis Start from the near end to determine the priority, then to the far end.
HO2C C H C C H CO2H
B
CO2H C
H H
CO2H
O2N CO2H
CO2H
Fischer Projection, popular in sugar chemistry, relate the config. at an assym. center to that of (+)glyceraldehyde, the standard
HO C HOH2C CHO H
D-(+)-glyceraldehyle
CHO H OH H CH2OH
CHO OH CH2OH
Rules C 1.most highly oxidized HOH2C CHO L-(-)-glyceraldehyle carbon on top. 2.vertical bonds CHO point backward 3.horizontal HO H bonds point forward CH OH
OH
D-erythrose
D
highest no.
H2N CH2OH CH2OH
L
CHO H R
D-threose
L-alanine
H HO HO H
CH 2 OH O H H OH OH
H HO H HO H
CH 2 OH O H H OH H
OH
CH H OH H H OH
-D-Glucopyranose
2 OH
-D-Glucopyranose
O H
H OH
OH
epi
CHO HO HO H HO H epimeric HO OH OH CH2OH HO H CHO H H H OH CHO
D-(+) Talose
CH3
CH3
erythroCHO H H OH OH CH2OH
threoCHO HO H H OH CH2OH
H3CS
Similar to threose
OH CH2OH NH2
CH2OH H2N H H OH
SCH3
D-Erythrose
D-Threose
Threo-(1R,2R)-2-amino-
close a reference
t-4-bromo-c-4-chloro-1-methyl-rcyclohexanecarboxylic acid
Alkene cis,trans based on the shape of the molecules E, Z based on priority rule used for R,S.
A
H 3C H
CO 2 H Cl
Cl Br
CH 3 I
cisE-
Z-
OH N H 3 CH 2 C H 3 CH 2 C N OH
anti-propiophenone oxime E-
i n si
de
exo, endo-2,4-dimethyl
H Cl
exo, exo-2,4-dimethyl
exo exo
HN AcO H OH
inside
endo-2-chloronorbornane
H HO HO H
6-exo-(acetyloxy)-8azabicyclo-[3.2.1]octan2-exo-ol
3--Cholestanol
3- -Cholestanol
Stereoselective ReactionA reaction in which one stereoisomer (or pair of enantiomer) is formed or destroyed at greater rate or to a greater extent than other possible stereoisomer.
O LAN H OH HO H
90%
HCO2H O OCH
CH3 H Ph CHO CH3MgI H Ph CH3 OH H CH3
10%
CH3 OH H Ph H CH3
erythro 67%
threo 33%
Stereospecific ReactionA reaction in which stereoisomerically different reactants yield stereoisomerically different products.
H3C Br Ph H H3C Ph H H H Ph OTs NaSPh H H3C TsO H NaSPh C H3C CH3 CH3 H H3C C CH3 CH3 C CH3 CH3 H H3C H C CH3 CH3 PhS H Br KOCH2CH3 Ph KOCH2CH3 H3C Ph Ph H
H3C Ph H
H Ph
SPh
H OH
OH
homotopic
HO
HO
HO H H
OH
H HO D
D OH H
pro- S
heterotopic
OH H3C
re
clockwise
si
H
OH H3C H
si
Vinylmagnesium bromide
Counter clockwise
Optical Activity
Enantiomers can exhibit optical activityrotation of plane polarized light. The two enantiomers rotate light to opposite direction, but to the same magnitude. rotation clockwise (d) counterclockwise ( l) for pure +)-glyceraldehyde, specific rot. +14 for a mixture of enantiomeric glyceraldehyde giving +12.6, 12.6 the excess is = 90% 95%+-and 5% --cpd.
14
Fischer assigned
H HO
OH H CO2H
(+)-Tartaric acid
confirmed by X-ray
correlating
C O 2H H 2N H C H 2O C O C H 2N H 2 H 2N C O 2H H C H 2O H
chlorination rxn H 2N
C O 2H H C H 2C l
(S)-()-Azaserine
(S)-()-Serine
by X-ray by exptl
the bonds connected to chiral center are not broken the abs. configuration remains.
CO 2 H Cl H CH 3
OHinversion
CO 2 H H OH CH 3
(S)-()-2-Chloropropanoic acid
(R)-()-Lactic acid