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Stereochemistry
Constitutional isomers Stereoisomers Mirror Images Chiral and Achiral Molecules Chirality and Symmetry elements

Stereochemistry
Chemistry of three dimensional structure of molecules.

Foundations laid by Jacobus vant Hoff and Joseph Achille Le Bel in 1874. Proposed independently that four bonds to carbon directed toward corners of a tetrahedron. Consequently, two compounds may be different because arrangement of their atoms in space is different.

Isomers are different compounds that have the same molecular formula. Constitutional isomers are isomers that differ because their atoms are connected in a different order. Molecular Formula C4H10 CH3CH2CH2CH3 Butane C3H7Cl CH3CH2CH2Cl 1-Chloropropane Constitutional isomers
CH3 H3C C CH3 and H Isobutane Cl H3C C CH3 and H 2-Chloropropane

C2H6O
CH3CH2OH Ethanol and CH3OCH3 Dimethyl ether

Stereoisomers differ only in arrangement of their atoms in space.

Cl Cl

C C

H H

Cl H

C C

H Cl

cis-1,2-Dichloroethene (C2H2Cl2)

trans-1,2-Dichloroethene (C2H2Cl2)

Me

Me

H
Me

Me

cis-1,2-Dimethylcyclopentane (C7H14)

trans-1,2-Dimethylcyclopentane (C7H14)

Constitutional isomers have:

different IUPAC names;
the same or different functional groups; different physical properties, so they are separable by physical techniques such as distillation; and different chemical properties. They behave differently or give different products in chemical reactions.

Stereoisomers differ only in the way atoms are oriented in

space.

Stereoisomers have:
identical IUPAC names (except for a prefix like cis- or trans-). Because they differ only in the three dimensional arrangement of atoms, stereoisomers always have the same functional group(s). A particular three-dimensional arrangement is called a configuration. Thus, stereoisomers differ in configuration, e.g., cis and trans isomers.

Problem: Classify each pair of compounds as constitutional

isomers or stereoisomers.

a) O

and

2,3-dimethylpentane and 2,4-dimethylpentane. different connectivity of atoms different names, therefore,

constitutional isomers

b)

and and

OH

four-membered ring and three-membered ring, different connectivity of atoms constitutional isomers different connectivity of atoms constitutional isomers trans isomer and cis isomer Both are 1,2-dimethylcyclobutane, but the CH3 groups are oriented differently. stereoisomers

c)

d)

and

Mirror Images Chiral and Achiral Molecules

Are you right-handed or left-handed? Handedness plays a surprisingly large role in your daily activities. Everything has a mirror image. Whats important in chemistry is whether a molecule is identical to or different from its mirror image. Some molecules are like hands. Left and right hands are mirror images of each other, but they are not identical.

 Hands look similar, yet a left-handed glove does not fit the right hand. Same principle applies to feet. Relationship between your two hands or your two feet is that they are non-superimposable (non-identical) mirror images of each other.
Objects that have left-handed and right-handed forms are called chiral (cheir, rhymes with "spiral"), the Greek word for handed.

To superimpose an object on its mirror image means to align all parts of the object with its mirror image.

 A mirror image is the reflection of an object in a mirror.

Super-imposable mirror images are images that coincide at all points when the images are laid upon each other. Non-superimposable mirror images are images where not all points coincide when the images are laid upon each other, and called enantiomers.

Human hands are non-superimposable mirror images.

Like human hands, all objects with non-superimposable mirror images exist in left-handed and right-handed forms.

Chirality is the concept of handedness as applied to molecules. Any organic molecule that contains a carbon atom with four different groups attached to it in a tetrahedral orientation possesses handedness. Such a carbon atom is called a chiral centre. A chiral centre is an atom in a molecule that has four different groups tetrahedrally bonded to it. A molecule that contains a chiral centre is said to be chiral.

A chiral molecule is a molecule whose mirror images are not superimposable. Chiral molecules have handedness.
An achiral molecule is a molecule whose mirror images are superimposable. Achiral molecules do not possess handedness.

Molecules of the general type shown below are chiral when W, X, Y and Z are different.

X W

* C
Z

In 1996, IUPAC recommended that a tetrahedral carbon atom that bears four different atoms or groups be called a chirality centre, and be identified by an asterisk (*). Several earlier terms, including asymmetric centre, asymmetric carbon, stereogenic centre, stereocentre, are still widely used.

Symmetry and Chirality

Symmetry is a part of our everyday lives in countless different ways, and although we may not have appreciated it, we are accustomed to beings surrounded by regular or symmetrical objects and arrangements of objects. We associate symmetry with beauty and harmony in nature. Here we examine only those aspects of chemistry, namely; symmetry elements; where symmetry is of particularly great importance.

Dictionary definitions of the word symmetry include: 1. similarity of form or arrangement on either side of a dividing line or plane; 2. excellence or beauty of form or proportion as a result of the similarity of form or arrangement. The word symmetry is derived from Greek and Latin words which mean measure together.

Thus, symmetry referred specifically to the similarity relative to a mirror plane.

A beaker or conical flask reflected through a mirror (a mirror plane or a plane of symmetry) might be identical to the other side of the beaker or conical flask.

 Most leaves have mirror planes. Many flowers have mirror planes too.

We associate symmetry with beauty and harmony in nature.

The symmetry element shared by most animals, birds, and fish is the mirror plane.

Some examples from organic chemistry:

Me Me

H
Me

Me

H CH3

CH3

H
H

CH3 H H CH3

CH3 CH3

Symmetry Elements and Symmetry Operations

A symmetry element is an imaginary line, plane, or point in a molecule with respect to which one or more symmetry operations may be carried out. A symmetry operation is a movement of the molecule, which results in a configuration that is indistinguishable from the original one (although not necessarily identical to it). Plane of Symmetry - Imaginary line through which reflection may be carried out. Divides molecule into equivalent halves. Like a mirror placed so that half the molecule is a mirror image of the other half.
H
Plane of Symmetry?

CH3 H

CH3

CH3 CH3

Centre (point) of symmetry or Centre of Inversion is a point in the centre of a molecule to which a line can be drawn from any atom such that, when extended an equal distance past the centre, the line meets another atom of the same kind.

H COOH

COOH H

H COOH

COOH H

centre of inversion H COOH COOH H

Molecules with a plane or centre of symmetry have superimposable

mirror images; they are achiral