Chemistry I (Organic): Stereochemistry

Diastereoisomers
Dr Alan Spivey; Office: 834 C1; e-mail: a.c.spivey@imperial.ac.uk; Tel.: 45841

Diastereoisomers:

Diastereoisomers (sometimes called diastereomers) are stereoisomers that are not enantiomers.
A common way of generating diastereoisomers is to put two (or more) stereogenic centres in the
same molecule.

NB. Epimers are diastereoisomers differing in configuration at just one stereogenic centre.

Unlike enantiomers, diastereoisomers have different chemical and physical properties (e.g.
melting points, solubilities, reactivities etc.). This is because the ways in which the electrons
associated with the various groups buttress against each other are different in the different
diastereoisomers, giving rise to diferent energies and different shapes.

For a molecule containing n stereogenic centres there are a maximum of 2n stereoisomers.

The following discussion is restricted to examples containing 2 stereogenic centres. There are two
cases:

1) The two stereogenic centres have different sets of groups attached.

e.g. pentane-2,3-diol

H OH Me H OH Me
Me 2 = HO H Me 2 = HO H
3 Et diastereoisomers 3 Et
H OH HO H HO H H OH
Et Et
(2R,3R) (2S,3R)

enantiomers diastereoisomers enantiomers

HO H Me HO H Me
Me H OH diastereoisomers H OH
2 = Me 2 =
3 Et 3 Et HO
H OH H
HO H Et H OH Et
(2S,3S) (2R,3S)

i.e. 4 stereoisomers, two pairs of enantiomers.

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2) The two stereogenic centres have the same set of groups attached.
e.g. tartaric acid (2,3-dihydroxybutan-1,4-dioic acid)

HO H CO2H CO2H
HO H
HO2C 2 H OH H OH
3 CO2H = HO2C 2 =
H OH
3 CO2H
HO H HO H
CO2H H OH
CO2H
(2R,3R) (2S,3R)

H
HO2C CO2H
enantiomers OH CO2H
diastereoisomers
HO
H HO HH
HO2C OH

H OH CO2H
H OH CO2H
HO2C 2 HO H
3 CO2H = HO H
HO H HO2C 2 =
H OH 3 CO2H H
CO2H OH
HO H CO2H
(2S,3S) (2R,3S)

meso-isomer
CHIRAL ACHIRAL

i.e. 3 stereoisomers, one pair of enantiomers (chiral) and a meso isomer (achiral).

Additional stereogenic centres add additional complexity – the maximum number of stereoisomers
is always 2n, where n is the number of stereogenic centres, but any isomers having an improper
rotation axes will be achiral (i.e. meso, as above).

Definition: meso is a stereodescriptor for an achiral member of a set of diastereoisomers that also
includes at least one chiral member.

Prochirality:
• Enantiotopic groups/substituents
• Diasterotopic groups/substituents
• pro-R and pro-S sterodescriptors
• Re and Si faces of e.g. carbonyl groups

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