CHAPTER 7

STREOCHEMISTRY

CHIRALITY
• Chiral – not identical with its mirror image – nonsuperimposable mirror image

Achiral – has superposable on their mirror images

Streoisomers with one chiral Carbon Atom
• Assymeric carbon – 4 different gp’s bonded to the carbon

• Chirality center

•Physical properties: MP, BP and refractive point are identical. •They differ in direction in the plane polarized light. •Right – dextrorotatory (D): left –levorotatory (L) •50/50 mixture of enantiomers – racemic mixture •Molecules (nonsuperimposable, produce measurable rotation in plane polarized light) =chiral molecule or optically active.

How to express the configuration of enantiomers in 3D??
4) A tetrahedral model of a chiral carbon atom (3 atoms will be a ‘base” of the pyramid. Rotate the model upward, so 2 atoms are sticking out toward you horizontally and other 2 atoms are directed vertically away from you. The 2 horizontal atoms – wedges. projected out of the paper The 2 vertical atoms – dashes. projected behind the plane of paper.

5)

6) 7)

Stereoisomers With Two Different Chiral Carbon Atoms

Van’t Hoff rule : 2n 12 and 34 are enantiomers 13,14, 23, 24 are diastreoisomers (stereoisomers that are not mirror image)

Molecules with two similar Chiral Carbon Atoms

180o

Meso compound

Streoisomerism in Cyclic compound

• Cis isomer = meso compound

• Trans isomer = enantiomeric compound

Specific Configuration
R and S designation – Cahn-Ingold-Prelog System
3) 4) 5) Groups connected to the chiral carbon are assingned priorities (atomic number) Lowest priority is put directed away from the observer. The remain 3 groups are projected toward the observer. If the molecule moves in clockwise – R; counterclockwise - S

Determining Group Priorities
Cl I H2 C H2C C CH2 CH2 CH3 CH2 Br

Cl > CH2Br > CH2CH2I > CH2CH2CH3
If rotates clockwise – R; anticlockwise = S

How to determine R and S configuration

Streoisomerism in Chemical Reaction • Meso Compound – hydroxylation and hydrogenation

• A pair of Enantiomers

• A pair of diastreoisomers