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Stereochemistry
Stereochemistry or 3D chemistry: Study of the relative spatial arrangements of atoms that form the
structure of a molecule.
Isomers: Molecules with the same molecular formula but with a different arrangement of their atoms.

Chain isomers: straight chains vs branched chains

Position isomers: differ in location of functional group
Functional isomers: differ in functional group (e.g. aldehydes and ketones)

Stereoisomers
Conformational isomers
Conformations: Different three dimensional arrangements of atoms that result from rotation about a
single bond
σ bonds can rotate freely, no change in overlap of sp 3
orbitals
Staggered vs eclipsed: as staggered means bonds are farther
apart, they are more stable
< torsional strain: repulsion of electrons in bonds
Projections: sawhorse – Newman – hashed-wedge

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Butane: 3 C-C bonds

< steric strain: crowding / hindrance of groups in a conformation

Cycloalkanes
< angle strain: optimal C-C bond is 109.5o ≠ optimal regular polygon angle

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Configurational isomers
Cannot interconvert between isomers without breaking a bond
Caused by double bond / chiral center (C atom with 4 different partners)
Cis-trans isomers (E-Z)
The molecule has an E configuration (entgegen) if the substituents of higher priority are on the opposite
side (trans) of the molecule.
The molecule has a Z configuration (zusammen) if the substituents of higher priority are on the same side
(cis) of the molecule
Rules of priority:
1. Rank the atoms directly attached to each carbon atom in the double bond in the order of
atomic number (highest number, highest priority).
2. If the two atoms attached are the same, than rank the second, third, etc. atom (first point of
divergence).
3. If substituents have double or triple bonds, treat them as if they were linked to two or three
single bonded atoms.
Chiral isomers
Isomers with chiral centers are asymmetrical molecules without a plane of center of symmetry
Enantiomers have identical chemical properties but they can differently rotate the plane of plane-
polarized light. Enantiomers are mirror images of each other.
Enantiomers:
Same physical activity
Opposite optical activity
Different biological activity
Naming of chiral centers: CIP system – R / S nomenclature
1. Rules of priority
2. Orient molecule so that lowest priority group is pointing away
3. Draw a curve from the highest priority, 1, to priority 2 and 3. If 1 > 2 > 3 is clockwise, the
chiral center has the R (rectus) configuration. If anti-clockwise the S (sinister) configuration.
Diastereomers: stereoisomers with more than one chiral centers
that are not mirror images.
Maximum number of stereoisomers of a molecule with n chiral
centers is 2n
Meso compounds: diastereomers with internal plane of symmetry
Correlation specific optical activity ([ α ]) and
observed optical activity (α ):

[ α ]D = (
α deg∗mL
c∗l g∗dm )

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If both enatiomers are present in a 1 : 1 ratio the solution is called a racemic mixture (racemate). NB the
solution is not optically active

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