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CHEM 109A
Organic Chemistry

https://labs.chem.ucsb.edu/zakarian/armen/courses.html

Chapter 4
Isomers
The arrangement of atoms in space

Problem 81. One of the chair conformers of cis-1,3-

dimethylcyclohexane is 5.4 kcal/mol less stable than the
other. How much strain energy does the1,3-diaxial interaction
introduce?

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Isomers
Isomers are compounds with different structures but the same molecular formula.

isomers

constitutional isomers stereoisomers

(different bond connectivity) (same bond connectivity, different configuration
(different 3D arrangement))
OH
O

C 3H 8O
enantiomers diastereomers
(isomers that are (isomers that are not
mirror images) enantiomers)
E or Z, cis or trans,
one asym. center: R vs. S
RSR vs RRR,
two or more: RR vs. SS
etc.
RSR vs. SRS
etc.
meso compounds

cis–trans: Diastereomers
will always have hydrogens

H H H

H
H’s are
still
H there

cis trans

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Which is Cis and Which is Trans?

E–Z: Diastereomers
which group is the higher
priority at this carbon? and this carbon?

lower priority

higher priority
H’s are
still
there

Z E

•  priority is determined by atomic weight; if same, move to the next heaviest atom

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E and Z Isomers

E and Z Isomers

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Chiral and Achiral Objects

A chiral object has a nonsuperimposable mirror image.

An achiral object has a superimposable mirror image.

Chiral and Achiral Objects

no plane or center of symmetry: chiral

if there is a center of symmetry, or a plane of symmetry:

achiral

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Enantiomers

Enantiomers are
nonsuperimposable
mirror images.

Chiral and Achiral Molecules

A chiral compound has a nonsuperimposable mirror image.

An achiral compound has a superimposable mirror image.
(it and its mirror image are identical molecules).

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Enantiomers

The two stereoisomers are called enantiomers.

Enantiomers are different compounds: they can be separated.
Enantiomers have the same physical and chemical properties.
(except: 1. rotation of polarized light; 2. When react with other
enantiomeric compounds)

Enantiomers

HO OH

O H H O
N N

HO OH

(-)-morphine (+)-morphine
binds to opioid receptors in the brain does not binds to opioid receptors
in the brain

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Compounds with an Asymmetric Center

Compounds with an Asymmetric Center

Problem 69. How many asymmetric centers does Mecavor have?

HO O

O
O

Mecavor

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Asymmetric Center versus Stereocenter

Asymmetric center: an atom attached to four different groups.

Stereocenter: an atom at which the interchange of two groups
produces a stereoisomer.

How to Draw Enantiomers

Perspective formulas

Br Br
Skeletal structures

Fischer projections

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R and S configuration. Naming Enantiomers

Assign relative priorities to the four groups.

R and S configuration. Naming Enantiomers

Draw an arrow from 1 to 2 to 3.

If the lowest priority group is on a hatched wedge, then

clockwise = R
and
counterclockwise = S

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Naming Enantiomers

If the lowest priority group is on a vertical bond, then

clockwise = R
and
counterclockwise = S

Naming Enantiomers

If the lowest priority group is on a horizontal bond, then

counterclockwise = R
and
clockwise = S

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Plane-Polarized Light

An Achiral Compound is Optically Inactive

An achiral compound does not rotate the plane of polarization

of plane-polarized light.

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A Chiral Compound is Optically Active

A chiral compound rotates the plane of polarization

of plane-polarized light.

If it rotates the plane clockwise = (+)
If it rotates the place counterclockwise = (–)

R and S versus (+) and (–)

Some R enantiomers are (+) and some are (–).

Some S enantiomers are (+) and some are (–).

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A Polarimeter

If One Enantiomer is (+), the Other is (–)

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Enantiomeric Excess
Enantiomeric excess tells us how much of an
excess of one enantiomer is in a mixture.

For example, if the sample of 2-bromobutane has an observed specific rotation

of +9.2, then the enantiomeric excess is 40%. In other words, the excess of one
of the enantiomers comprises 40% of the mixture.

Compounds with Two Asymmetric Centers

maximum # of stereoisomers = 2n

(n = # of asymmetric centers)

1 and 2 are enantiomers. 3 and 4 are enantiomers.

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Diastereomers: stereoisomers that are not

enantiomers

1 and 2 are enantiomers. 3 and 4 are enantiomers.

Diastereomers are stereoisomers that are not enantiomers.

1 and 3 are diastereomers. 2 and 3 are diastereomers.
1 and 4 are diastereomers. 2 and 4 are diastereomers.

Diastereomers have different physical and chemical properties.

Perspective Formulas of the

Four Stereoisomers

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Two Asymmetric Centers,

Four Stereoisomers

The cis stereoisomers are a pair of enantiomers.

The trans stereoisomers are a pair of enantiomers.

Identifying an Asymmetric Center

An asymmetric center is attached to four different groups.

two asymmetric centers, four stereoisomers

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No Asymmetric Centers

There are only two stereoisomers: cis and trans.

No Asymmetric Centers

There are only two stereoisomers: cis and trans.

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Two Asymmetric Centers: Three Stereoisomers

(a Meso Compound and a Pair of Enantiomers)

A Meso Compound Has a

Superimposable Mirror Image

Meso compounds are optically inactive

even though they have asymmetric centers.

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A Meso Compound Has a Plane of Symmetry

A Meso Compound

A compound with two asymmetric centers that has

the same four groups bonded to each asymmetric center
will have three stereoisomers:

a meso compound and a pair of enantiomers.

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A Meso Compound

For cyclic compounds with the same substituents bonded to

two asymmetric centers,
cis = a meso compound
and
trans = a pair of enantiomers.

Naming Stereoisomers

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Naming Stereoisomers

Naming Stereoisomers

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Physical Properties of Stereoisomers

Nitrogen and Phosphorus Can Be

Asymmetric Centers

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Amine Inversion

If one of the four groups attached to N is a lone pair,

the enantiomers cannot be separated,
because they interconvert as a result of amine inversion.

A Receptor is a Protein
Proteins are Chiral Molecules
Because a receptor is chiral, it binds one enantiomer.

A right-handed glove fits only a right hand.

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A Receptor Binds One Enantiomer

Each enantiomer binds to a different receptor in the nose.

Physiological Properties of Enantiomers

Enantiomers can have very different

physiological properties.

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Separating Enantiomers

separating by hand

separating by chromatography

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