CHM 303A/401A - Organic Chemistry - I
D r. Pa r t h as ara thi Su b r a ma n ian
D e pa rtment of C he mis try
IIT K a n p u r
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References
Advanced Organic Chemistry Part A: Structure and Mechanisms
- Francis A. Carey, Richard J. Sundberg
Advanced Organic Chemistry Part B: Reaction and Synthesis
- Francis A. Carey, Richard J. Sundberg
Transition Metals in the Synthesis of Complex Organic Molecules
- Louis S. Hegedus, Björn C. G. Söderberg
March's Advanced Organic Chemistry: Reactions, Mechanisms
and Structure
- Michael B. Smith, Jerry March
Organic Chemistry: Second Edition
Jonathan Clayden, Nick Greeves, Stuart Warren
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Importance of Stereochemistry
caraw ay seeds spearmint
enantiomers
configurational Isomers 3
Importance of Stereochemistry
analgesic drug antitussive drug
(pain killer) (cough suppressant)
Synthetic drug molecules
Only D-Saccharide Only
L-Amino acids
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Bonding and Structure of Organic Molecules
There are three hybridization states and geometries.
❖sp3 Tetrahedral
Methane, CH4 Tetrahedral
❖ sp2 Trigonal planar
❖ sp Linear
Formaldehyde, CH4
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Conformations
• Conformations are different spatial arrangements of atoms in a molecule that
are interconverted by rotation about single bonds.
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Stereochemical Representation
Ethane
• Two sp3 hybrid carbons.
• Rotation about the C—C sigma bond can occur.
Ethane-Wedge Structures Ethane- Sawhorse Projection
• Sawhorse projection, allows better visualization of the three‐dimensional geometry
between adjacent carbon atoms
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Stereochemical Representation
Viewed from the front carbon to the back through the C-C bond
• The Newman projection is a convenient way to judge the stability of the different
conformations of a molecule.
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Conformations
• Conformers are named as “Eclipsed and Staggered”
• In the eclipsed conformation, the C—H bonds on one carbon are directly
aligned with the C—H bonds on the adjacent carbon.
• In the staggered conformation, the C—H bonds on one carbon bisect the
H—C—H bond angle on the adjacent carbon.
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Dihedral Angle/ Torsional Angle
• Dihedral angle is the angle between two
intersecting planes.
• For example, the angle f is the dihedral angle
between the H1-C2-C3 plane and the C2-C3-H4
plane.
• Torsional angle is an alternative term used for dihedral angle.
• While dihedral angle is measured as 0-360º, torsional angle is
measured as 0-180º
• A positive value in the clockwise direction and a negative value
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in the anti-clockwise direction. 10
How to Draw Newman Projections
Step 1. Look directly down the C—C bond (end-on) and draw a circle with a dot in
the center to represent the carbons of the C—C bond.
Step 2. Draw in the bonds.
Draw the bonds on the front C as three lines meeting at the center of the circle.
Draw the bonds on the back C as three lines coming out of the edge of the circle.
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Naming in the Newman projections
syn-periplanar syn-clinal
anti-clinal
anti-periplanar
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Naming terminologies in conformations
• Staggered - A low energy conformation where the bonds on adjacent atoms bisect
each other (60º dihedral angle), maximizing the separation.
60º
• Eclipsed - A high energy conformation where the bonds on adjacent atoms are
aligned with each other (0º dihedral angle).
0º
• Gauche - Description given to two substitutents attached to adjacent atoms when
their bonds are at 60º with respect to each other.
60º
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Strain in Organic Molecules
Three types of strains:
1. Steric, 2. Torsional and 3. Angular strain
Steric (non-bonded interactions) – Destabilization due to the repulsion between the
electron clouds of atoms or groups. Groups compete to occupy common space. Strain
due to close contact of atoms separated by four or more bonds
Torsional – Strain resulting from eclipsing interactions between bonds on adjacent
carbon atoms. Actual reasons are highly debated.
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Torsional & Angular Strain
Angular – Destabilization due to distortion of a bond angle from its optimal value
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Conformations of Ethane
2.9
kcal/mol
• The torsional energy of ethane is lowest in the staggered conformation. The eclipsed
conformation is about 2.9 kcal/mol (12.6 kJ/mol) higher in energy.
• At room temperature, this barrier is easily overcome, and the molecules rotate
constantly.
• There are infinite number of conformations possible in between both these
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conformers 16
Conformations of Propane
• Propane is shown here as a perspective drawing and as a Newman projection looking
down the C1—C2 bond.
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Conformations of Propane
• The staggered conformations of
propane is lower in energy than the
eclipsed conformations.
• Since the methyl group occupies
more space than a hydrogen, the
torsional strain will be 0.4 kcal/mol
higher for propane than for ethane.
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Conformation Of Butane
60° 60° 60° 60° 60° 60°
syn- gauche anti- gauche syn-
periplanar anticlinal periplanar anticlinal periplanar
synclinal synclinal
0° 60° 120° 180° 240° 300° 360°
Eclipsed Staggered Eclipsed Staggered Eclipsed Staggered Eclipsed
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Gauche Butane Interaction
syn- anticlinal
periplanar 3.6 kcal/mol
5.0 kcal/mol
anti- synclinal
periplanar gauche
0.0 kcal/mol 0.9 kcal/mol
Boltzmann population 69% Boltzmann population 31%
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Conformation of Butane
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