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Asymmetric Synthesis Lec 3

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34 views

Asymmetric Synthesis Lec 3

Uploaded by

vaibhavizende9159
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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14-10-2021

Q1. Identify the type of selectivity involved in the following reaction

PCM_SPC 1

PCM_SPC 2

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PCM_SPC 3

PCM_SPC 4

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PCM_SPC 5

PCM_SPC 6

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PCM_SPC 7

Summary

PCM_SPC 8

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PCM_SPC 9

Enantiomeric excess is defined as the proportion of the major


enantiomer produced, less that of the minor enantiomer.
For Example 3:1 mixture of enantiomers (75% : 25%) has an ee of 75 – 25
= 50%
An enantiomeric excess 70% means Major isomer = 85% and Minor
isomer = 15%
Therefore ratio the enantiomer is 85% : 15%

Enantiomeric excess 98% means ratio of enantiomers is 99:1

Enantiomeric excess = 99% means major isomer 99.5% and minor


isomer 0.5%

ee = 100% indicates only one isomer in 100%

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DETERMINING ENANTIOMER COMPOSITION


The composition of enantiomers is described by optical purity
Optical purity is the ratio of observed specific rotation to the maximum or
absolute specific rotation of a pure enantiomer sample.
If the optical rotation of pure enantiomer is known, the ee value may be
determined directly from the observed optical rotation

[α]
[α]20
Where [α] is the measured rotation; L is the path length of cell (dm); c is
concentration (g/100 ml); D is the D line of sodium, the wave length of
light used for measurement (5983Ǻ); and 20 is the temperature in degrees
(Celsius)

Optical purity (%) = [α]obs / [α]max X 100

DETERMINING ENANTIOMER COMPOSITION


The presence of an asymmetric carbon is neither a necessary nor a
sufficient condition for optical activity.
Each enantiomer of a chiral molecule rotates the plane of polarized light to
an equal degree but in opposite directions.
A chiral compound is optically active only if the amount of one enantiomer
is in excess of the other.
The enantiomer composition of a sample may be described by the enantiomer
excess (ee), which describes the excess of one enantiomer over the other

[R] and [S] are the composition of R and S enantiomers, respectively.


Mole fraction of major enantiomer
Enantiomeric excess = X 100
Mole fraction of minor enantiomer

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The diastereomer composition of a sample can be described by the


diastereomeric excess (de), which refers to the excess of one
diastereomer over the other:

where [SS] and [SR] are the composition of the Diastereomers,


respectively

Measuring of Enantiomeric Excess (ee)


One way is to measure an angle through which a sample rotates plane
polarized light. The angle is proportional to enantiomeric excess of the
sample

The limitation of this method is that to measure actual value for ee you
need to know what rotation of a sample of 100%ee gives and that is not
always possible.
The polarimeter measurements are unreliable they depends on
temperature, solvent, concentration and subject to massive error
HPLC: Less than a milligram of chiral compounds can be passed down
through a narrow column containing chirally modified silica. The two
enantiomers are separated and the quantity of each can be measured and
ee derived.

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Gas chromatography is also used in the same way only the column is
packed with stationary phase such as isoluecien derivatives.
Spectroscopic methods can also be used to determine e.e. if
compound is alcohol or amine
• Alcohol + Mosher’s acyl chloride ester derivative
• Amine + Mosher’s acyl chloride amide derivative

• Mosher’s acyl chloride

• Two products becomes Diastereomers and gives different NMR

• Another powerful method of discriminating between


enantiomers is to add an enantiomerically pure
compound to the NMR sample that forms the complex
with compounds
The complexes formed from enantiomers are
diastereomeric and therefore have different chemical
shifts. By integrating the NMR signals, the ratio of
enantiomers can be determined.

Resolution can be used to separate enantiomers

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First Generation: Substrate controlled reaction:


1. S* R P*
S X* R P* X *
Second Generation: Auxiliary controlled methods
A* R - A*
2. S S A* P* A* P*
Third Generation: Use of chiral reagents
R*
3. S P*
R*
S* P*
Fourth Generation: Use of chiral catalyst or ligands
R
4. S P*
C at *
S R P*
C at/L *PCM_SPC 17

What is the relationship between the indicated groups in the following


molecules

PCM_SPC 18

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