2103BPS CYCLE 3

STEREOCHEMISTRY AND ALKYL HALIDES

Lecture 1 Lecture 2 Workshop Tutorials QUIZ

1 April 13 April 15 April 13 and 15 April 20 April

Stereochemistry Chapter 9
1. STEREOCHEMISTRY

Tetrahedral centers with 4 different groups attached will have a mirror image which is different (compare left and right hands). Mirror-image isomers are called enantiomers. Molecules that exist in enantiomeric forms are said to be chiral.

Chiral Molecules Non-superimposable mirror images Exist in two different enantiomeric forms

A molecule is not chiral if it contains a plane of symmetry

Enantiomers and Absolute configuration R/S convention 1. Rank the atoms attached to the stereogenic center according to atomic number; the higher the atomic number, the higher the priority. 2. If a decision cannot be reached in step 1, work outward from the stereogenic centre until a decision is reached.

3. Place the lowest priority group to the back. With the remaining three groups, working from highest to lowest priority:

Example:

The sign of optical rotation , (+) or (-) is not related to the R, S designation.

Levorotatory (-) eg (-)-Morphine Dextrotatory (+) eg (+) Sucrose

Different types of Isomers

Diastereomers More than one centre of chirality Stereoisomers that are not mirror images Example: 2-amino-3-hydroxybutanoic acid (threonine)

RR

SS

RS

SR

RR
diastereomers

enantiomers

ers eom ter dias diast ereo mers

SS
diastereomers

RS

enantiomers

SR

Meso Compounds Compounds that have chirality centres but that are achiral due to a plane of symmetry are called meso compounds

Racemic Mixtures

Fisher Projections
COOH H C CH 3 HO H COOH OH CH3 H COOH OH CH3

Fisher projection of (R)-Lactic Acid

Two allowed movements

COOH H OH CH3 HO CH3 H COOH

180o rotation

COOH H OH CH3 HO

COOH CH3 H

hold one group steady and rotate other three groups clockwise or anticlockwise

2. ALKYL HALIDES Preparation Addition of Br2 to alkenes

Radical Halogenation of Alkenes Mechanism Figure 10.1

CH3 H3C CH CH3

Cl

2 h

CH3 H3C C Cl CH3

CH3 H3C CH CH2 Cl

Alkyl halides can be prepared by the free radical halogenation of hydrocarbons.

Results in mixtures of products Mono-, di-, and trichlorides etc Some hydrogens are more reactive than others.

H R C H 1o
<

H R C R 2o
<

R R C R 3o

stability and reactivity

Other preparations and reactions See summary sheet Alkyl halides can undergo: Substitution
Nu C X C N u + X

Elimination
Nu H X C C + N u H + X

SN2 reaction

SN2 reaction

SN1 reaction

SN1 reaction

E2 reaction

E1 reaction

The geometric requirement for E2 reaction in a cyclohexane

Summary of substitution and elimination

Halide Type RCH2X 1o

SN1
Does not occur

SN2
Highly favoured

E1
Does not occur

E2
Occurs when strong bases are used

R2CHX 2o

Can occur with benzylic and allylic halides

Occurs in competition with E2 reaction

Can occur with benzylic and allylic halides

Favoured when strong bases are used

R3CX 3o

Favoured in hydroxylic solvents

Does not occur

Occurs in competition with SN1 reaction

Favoured when bases are used