ISOMERISM

[CHEM30] Essentials of Organic Chemistry (Lecture)

UP College of Nursing (Block 3) | Prof. Nelson R. Villarante | 1st Sem 2022
Transcriber & Editor: VALERA, Katelyn B.

Trans Unit III: Isomerism

OUTLINE
DRAWING STRUCTURES 1
WEDGE 1
DASH 1
ISOMERS 1
CONSTITUTIONAL ISOMERS 1
STEREOISOMERS 2
Figure 2.0 - Examples of Isomers
CONFORMATIONAL ISOMERS 2
ENANTIOMERS OR OPTICAL ISOMERS 2 ● Isomers can be divided into the following:
DIASTEREOMERS OR CIS-TRANS ISOMERS 3 ○ Constitutional/structural isomers; and
SUMMARY 3 ○ Stereoisomers

CONSTITUTIONAL ISOMERS
DRAWING STRUCTURES
● Constitutional isomers are compounds with the same
● Wedge and Dash molecular formula but different connectivities.
○ Two other types of line bonds that depict the ● Constitutional isomers are divided into the following::
projection of the element or compound in a ○ Chain isomers
structure. ○ Positional isomers
○ Plays an important role in stereochemistry. ○ Functional isomers
○ Represents or interprets the three-dimensional
(3D) structure of a molecule.
CONSTITUTIONAL DESCRIPTION AND ILLUSTRATION
ISOMER TYPE
Chain Isomers Isomers that have the same formula
but different connectivity.

Example:

Figure 1.0 - Examples of Wedges and Dashes in a Structure

○ There can only be 1 wedge and 1 dash between 2

normal bonds within a plane.

WEDGE

● The bond is going out of the plane (toward the observer).

● Spatial arrangement.
● Represented by a thick, dark bond.

DASH

● Bond is going towards the plane (away from the observer;

into the paper).
● The implied hydrogen automatically gets a dashed bond
(but not in all cases).
● Represented by a bond made up of various dashes.
ISOMERS
● Isomers are compounds with the same formula but are
different from each other (either in connectivity or in the
spatial arrangement or projection).
● Isomers can have:
○ DIfferent connectivity of atoms; and
○ Same connectivity of atoms, but different
orientations in space.
Butane and isopentane, as well as
pentane, isopentane, and neopentane,
have the same formula, respectively.
The differences can be seen in the
attachment or connections of carbon
atoms.
Positional Isomers with the same functional group
Isomers but the position of the functional group
is different.
Example:

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 Lecture Topic: Isomerism

● Rules:
○ Look at the four atoms directly attached to the
chirality center and rank them according to
atomic number. The atom with the highest
atomic number will have the highest
priority/ranking, whereas the atom with the
Functional Isomers with the same molecular
lowest number will have the lowest ranking.
Isomers formula that have different functional
○ If a decision cannot be reached by ranking the
groups.
first atoms in the substituent, look at the second,
third, or fourth atoms until the difference is
Example:
found.

STEREOISOMERS

● Isomers with the same connectivity but different spatial

arrangement or orientation in space.
● In enantiomers, the difference in orientations will result in
the breaking of bonds around the central atom.

CONFORMATIONAL ISOMERS

● Also called conformers.

Figure 4.0 - Designation of Priority Atoms
● Isomers are formed due to the free rotation of a
carbon-carbon single bond.
○ After identifying the ranking, put the 4th rank
● Rotation of single bond results in the different orientations
(least) at the back of the atom or structure (if
of atoms in space.
needed) and count the other 3 and determine the
sequence.
■ R Configuration: Clockwise
■ S Configuration: Counterclockwise

Figure 3.0 - Conformational Isomers

ENANTIOMERS OR OPTICAL ISOMERS

● Mirror images of each other; nonsuperimposable.

● Optical activity is independent of absolute configuration.
● R, S configuration is designated per chiral center.
● Sequence rule for specifying absolute configuration is also
known as the Cahn-Ingold-Prelog System/Rules.

CAHN-INGOLD-PRELOG SYSTEM

● General method applies to the configuration at each

chirality.
● Configuration is specified by the relative positions of all
the groups with respect to each other at the chirality
center.
● Groups are ranked and compared in an established priority
sequence.

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 Lecture Topic: Isomerism

Figure 5.0 - The Single Swap Rule

(for determining S or R Configuration)

DIASTEREOMERS OR CIS-TRANS ISOMERS

● Isomers that are not mirror images of each other.

● Nonsuperimposable.
● Molecule with one chiral center can have an enantiomer (R,
S) but not a diastereomer.
● Epimers: Compounds in which two diastereomers differ at
only one chirality center but are the same at all the others.
● Diastereomers can have different physical properties and
reactivity.
● Can have two or more stereocenters.

Figure 6.0 - Comparison between Enantiomers and

Diastereomers

● Remember:
○ Enantiomers are non-superimposable MIRROR
IMAGES of each other.
○ Diastereomers are non-superimposable and are
NOT MIRROR IMAGES of each other.

SUMMARY

Figure 7.0 - Isomerism Flowchart