2302169 Chem Med Studt

1) Constitutional (Structural) Isomer VS Stereoisomer

STEREOCHEMISTRY

Constitutional isomer Stereoisomer -different IUPAC names -identical IUPAC names (except for a prefix like cis or trans) -same or different functional groups -same functional group(s) -different physical & chemical properties -different only in orientation in space (3D; configuration)

2) Stereochemistry

3) Chiral VS Achiral Molecule 3.1 Chiral molecule: Molecule or object that is not superimposible on its mirror image Chiral Achiral

2302169 Chem Med Studt

One stereogenic center (chiral center)

STEREOCHEMISTRY

No plane of symmetry

0 chiral center achiral molecule 1 chiral center chiral molecule 1 chiral center chiral or achiral molecule 3.2 How to draw tetrahedron

4) Enantiomers

2302169 Chem Med Studt

4.1 Labeling chiral centers with R or S (Cahn-Ingold-Prelog system) Assign a priority (1,2,3,4) to each group bonded to chiral center Use priority to label R or S isomer

STEREOCHEMISTRY

Priority Rule Rule 1: assign priorities (1,,4) to the atoms directly bonded to chiral center in order of decreasing atomic number
4 Atomic number: Br> Cl > F >H 3 2 H F C Br Cl 1

Rule 2: If two atoms on chiral center are identical, assign priority based on atomic number of the atoms bonded to these atoms. One atom of higher atomic number determines a higher priority

Rule 3: If two isotope are bonded to the chiral center,assign priorities in order of decreasing mass number.
4 1 Br H C Cl 2 D 3 heavier isotope

Rule 4: To assign a priority to an atom that is part of a multiple bond, treat a multiple bonded atom as an equivalent number of single bon atoms

Labeling R or S to Chiral Center Step 1: assign priorities from 1 to 4

2-butanol
1 OH 4 2 H C CH 2CH3 H 3C 3 A

1 OH Priority: -OH, -CH 2CH3, -CH 3, -H

4 C H 2 H 3CH 2C CH3 3 B

2302169 Chem Med Studt

STEREOCHEMISTRY

Step 2: orient the molecules with lowest priority (4) back and visual the remaining priorities (1-3)
1 OH Enantiomer A H C 3 H 3C 4 CH 2CH 3 2 eye 1 OH H 3C 3 CH 2CH3 2

1 OH Enantiomer B 4 C H 2 H 3 CH 2C CH 3 3 H 3CH 2C 2

1 OH CH 3 3

Step 3: Trace a circle from priority group 123

1 OH 3 H 3C CH 2CH 3 2 1 OH S-isomer 2 H 3 CH 2C CH 3 3 clockwise directiion R -isomer

Enantiomer A

counterclockwise directiion

Enantiomer B

5) Diastereomers 5.1 Configurational diastereomers

H 3CH2 C

* *

H H CH 3 Br Br chiral center, n = 2 max. stereoisomers = 4

2,3-dibromopentane

5.2 Cis-trans diastereomers

Alkene H3C H H CH 3 H3C H CH 3 H CH3 H H CH3 Cycloalkane CH3 H CH3 H

t rans -2-Butene

cis -2-Butene

t rans -1,3-dimethylcyclopentane

cis -1,3-dimethylcyclopentane

2302169 Chem Med Studt

6) Meso Compounds

STEREOCHEMISTRY

H 3C Br H C

CH 3 Br H

H 3C Br H D identical

CH 3 Br H

Isomers
diff erent compounds with the same molecular formula

Constitutional isomers
isomers having atoms bonded to diff erent atoms

Stereoisomers
isomers with a difference in 3D arrangement only

Enantiomers
mirror images

Diastereomers
not mirror images

Congifurational diastereomers

Cis-Trans diastereomers

7) Optical Activity of Stereoisomer

2302169 Chem Med Studt

7.1 Rotation of polarized light

STEREOCHEMISTRY

Achiral Molecule >> Optically Inactive

Chiral Molecule >> Optically Active

Two enantiomers: rotate plane-polarized light to an equal extent but in opposite directions. No relationship exists between R and S prefixes and the (+) and (-) designations that indicate optical rotation. 7.2 Specific rotation

7.3 Racemic mixture and enantiomeric excess (ee) : A mixture containing equal amount of two enantiomers. Denoted by the symbol ()

ee = % of one enantiomer - % of the other enantiomer ee = ([] mixture/[] pure enantiomer) x 100.