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Chapter 5: Stereochemistry! p.

159 - 189

Chapter 5

Stereochemistry: the 3D shape of a molecule" Why does 3D shape matter?! Biological systems are extremely selective and can distinguish between molecules with slight stereochemical differences." Thalidomide"


Chapter 5

Isomers: different compounds with the same molecular formula" Constitutional/Structural Isomers: isomers that vary in the way that atoms are connected to each other" Different nomenclature" Different physical and chemical properties" Sometimes different functional groups" Stereochemical Isomers (stereoisomers): isomers that vary only in the way that atoms are orientated in space" Geometric isomers: cis/trans isomers (one type)" Same nomenclature (only vary by cis/trans or R/S)" Most of the same physical and chemical properties" Same functional groups!

Chapter 5

Constitutional vs Stereoisomers!

Chapter 5

Chiral vs Achiral Molecules!

Everything has a mirror image what we care about is whether the mirror image is identical or different from the original"

Chiral: a molecule (or object) that is not superimposable on its mirror image!
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Achiral: a molecule (or object) that is superimposable on its mirror image!

Chapter 5

To Test for Chirality in Molecules!

Draw molecule in 3D (using wedges and dashed lines for front and back)" Draw its mirror image " Try to align all bonds/atoms (you can rotate the molecule but you cannot break bonds)" Try: H2O, CH2BrCl and CHBrClF "

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Achiral Molecules!

Chapter 5

Chiral Molecule!

The two molecules of CHBrCF (A & B) are stereoisomers." Enantiomers: a pair of molecules that are nonsuperimposable mirror images" Tetrahedral Stereogenic Center: a tetrahedral carbon atom bonded to four different groups (most chiral molecules contain one or more stereogenic centers)" Stereogenic Center: any site in a molecule at which the interchange of two groups for a stereoisomer!
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Stereogenic Centers!
Molecules with no stereogenic centers: " generally not chiral (few exceptions we will learn later)" Molecules with one tetrahedral stereogenic center: " always chiral" Molecules with two or more stereogenic centers:! may or may not be chiral (must examine further look at mirror image)" Stereogenic centers denoted using C*"

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Plane of Symmetry!
Plane of Symmetry: a mirror plane that cuts a molecule in half, so that one half of the molecule is a reection of the other half" Achiral molecule usually contain a plane of symmetry, but chiral molecules do not"

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Principles of Chirality!
Everything has a mirror image. The big question is whether a molecule and its mirror image are superimposable." A molecule is chiral if it is not superimposable on it mirror image." The terms stereogenic center and chiral molecule are related but distinct. In general, a chiral molecule must have one or more stereogenic centers" The presence of a plane of symmetry makes a molecule achiral."

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Drawing Enantiomers!
Find the tetrahedral stereogenic center" Draw molecule in 3D." Draw a mirror image of the original molecule (can be from any angle as long as you draw a reection of original molecule)"

Chapter 5


Stereogenic Centers in Cyclic Compounds!

To determine stereogenic centers in a ring, always draw the ring in a at orientation/conformation" Determine if carbon is bonded to four different groups"

Chapter 5


How many stereogenic centers?!

Simvasta:n Trade Name: Zocor

Chapter 5


R/S Nomenclature!
To name enantiomers we add R or S distinction to nomenclature that is based on assigning priorities to atoms" Assign Priorities (1-4) to atoms directly attached to the stereogenic center (highest priority => 1) " Priority goes to highest atomic number" With isotopes, heavier atom gets priority (3H > 2H > 1H)" With ties, use the next atom along the chain (priority assigned at rst point of difference)" Treat double and triple bonds as if each bond represented a separate atom bond"

Chapter 5


Assigning R and S!
Rotate molecule so that lowest priority group is in the back" Trace circle from 1-3" Clockwise circle => R! Counterclockwise circle => S"

Chapter 5


Molecules with two or more stereogenic centers may or may not be chiral" For n stereogenic centers, the maximum number of stereoisomers is 2n (although sometimes fewer)" Diastereomers: stereoisomers that are not mirror images of each other" Diastereomers have the same R/S designations for at least one stereogenic center and opposite for at least one stereogenic center"

Chapter 5


Meso Compounds!
Meso Compound: an achiral compound that contains tetrahedral stereogenic centers" Meso compounds generally contain a plane of symmetry "

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Disubstituted Cycloalkanes!
When determining chirality in cycloalkanes draw the rings as at molecules!

Cis isomer is a meso compound (plane of symmetry)"

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Summary of Isomers!

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Physical Properties of Enantiomers!

The chemical and physical properties of two enantiomers are identical except in their interaction with chiral substances" Physical: m.p., b.p., solubility" Chemical: same electrophilic/nucleophilic sites" Enantiomers differ by their interaction with plane-polarized light" Optical Activity: the ability of a molecule to rotate a plane of polarized light" Enantiomers will rotate a beam of plane-polarized light in equal but opposite directions" Each enantiomer is optically active " Clockwise rotation of light => Dextrorotatory (d or (+))" Counterclockwise rotation of light => Levorotatory (l or (-))" No relationship between R/S and d/l (nomenclature vs physical property)"

Chapter 5


Optical Activity!

Achiral molecules do not rotate light"

Chiral molecules rotate light and the rotation can be measured"

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Racemic Mixtures!
What about a 50/50 mixture of two enantiomers in solution" "optical activity = 0 " solution does not rotate a plane of polarized light" Racemic Mixture: optically inactive solution containing a 1:1 mixture of enantiomers racemate labeled: d,l or ()" Enantiomeric Excess (ee): when not purely one enantiomer in solution but no a 1:1 mixture there is an excess of one enantiomer in solution -> does rotate plane-polarized light" ee = % of enantiomer A - % of enantiomer B"

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Physical Properties of Diastereomers!

Diastereomers can have different chemical and physical properties including optical rotation"

Chapter 5