Chapter 4: Stereochemistry

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Chapter 4: Stereochemistry

Introduction To Stereochemistry Consider two of the compounds we produced while finding all the isomers of C 7 16 : C 3 C 3 2-methylhexane 3-methylhexane C 2-methylhexane Bu Bu mirror rotate Bu 2-methylhexame is superimposable with its mirror image

Introduction To Stereochemistry Consider two of the compounds we produced while finding all the isomers of C 7 16 : C 3 C 3 2-methylhexane 3-methylhexane C Et Et 3-methylhexane Pr Pr Et mirror rotate Pr 2-methylhexame is superimposable with its mirror image

Introduction To Stereochemistry Consider two of the compounds we produced while finding all the isomers of C 7 16 : C 3 C 3 2-methylhexane 3-methylhexane Compounds that are not superimposable with their mirror image are called chiral (in Greek, chiral means "handed") 3-methylhexane is a chiral molecule. Compounds that are superimposable with their mirror image are called achiral. 2-methylhexane is an achiral molecule. An atom (usually carbon) with 4 different substituents is called a stereogenic center or stereocenter.

Enantiomers Et Et C 3 3-methylhexane Pr Pr mirror enantiomers Et Et Pr Pr Two compounds that are non-superimposable mirror images (the two "hands") are called enantiomers.

Introduction To Stereochemistry Structural (constitutional) Isomers - Compounds of the same molecular formula with different connectivity (structure, constitution) 2-methylpentane 3-methylpentane Conformational Isomers - Compounds of the same structure that differ in rotation around one or more single bonds Configurational Isomers or Stereoisomers - Compounds of the same structure that differ in one or more aspects of stereochemistry (how groups are oriented in space - enantiomers or diastereomers) We need a a way to describe the stereochemistry! 3-methylhexane 3-methylhexane

The CIP System Revisited 1. Rank each substituent attached to the stereocenter according to the CIP priority system (1 = highest, 4 = lowest) 2 1 2 1 3 4 4 3 2. "View" the compound with the lowest priority substituent pointing away from you 2 1 2 Et 1 Pr 1 2 Pr Et 2 1 3 4 4 3 4 3 4 3 3. Draw a circular arrow from connecting substituents 1 3 from highest to lowest priority. If the arrow moves clockwise, the sterocenter is labeled (R) [this stands for rectus]. If the arrow moves counterclockwise, then the stereocenter is labeled (S) [this stands for sinister]. 1 2 2 1 Et Pr Pr Et 4 4 3 3 (S)-3-methylhexane counterclockwise clockwise (R)-3-methylhexane

The CIP System Revisited F 3 C C 3 C 3 3 C C 3 Br C 3 3 C C 3 C 3

The CIP System Revisited 1 F 3 C 3 4 2 C 3 F C 3 3 C (R)-2-fluorobutane 3 C 4 3 C 3 C 3 1 2 (S)-3-tert-butylcyclohexene 3 C 3 C 1 C 3 4 2 3 1 Br 4 3 2 C 3 3 C C 3 2 3 (S)-4-bromo-2-methyl-1-pentene C 3 1 4 (R)-2-hydroxy-2-methyl-butanal

Properties of Chiral Molecules Chiral objects can only be "recognized" as chiral by another chiral object Carvone Which is (S) and which is (R)? [Your nose can tell!] 2 3 4 1 Carvone 3 1 4 2 (R) (S)

Properties of Chiral Molecules Chiral objects can only be "recognized" as chiral by another chiral object Carvone Which is (S) and which is (R)? [Your nose can tell!] 2 3 4 1 Carvone 3 1 4 2 (R) (S)

Properties of Chiral Molecules Chiral objects can only be "recognized" as chiral by another chiral object (R)-carvone [odor of spearmint] (S)-carvone [odor of caraway seed]

Multiple Stereocenters 1 stereocenter: 2 stereoisomers (S)-3-methylhexane (R)-3-methylhexane 2 stereocenter: 4 stereoisomers 3(S), 4(S)-3-chloro-4-methylhexane 3(R), 4(S)-3-chloro-4-methylhexane 3(S), 4(R)-3-chloro-4-methylhexane 3(R), 4(R)-3-chloro-4-methylhexane

Multiple Stereocenters enantiomers 3(S), 4(S)-3-chloro-4-methylhexane 3(R), 4(R)-3-chloro-4-methylhexane What about these relationships? 3(R), 4(S)-3-chloro-4-methylhexane 3(S), 4(R)-3-chloro-4-methylhexane enantiomers Stereoisomers that are not enantiomers (non-superimposable mirror images) are called diastereomers

Multiple Stereocenters Br!!! C 3 3 stereocenters (R), (R), (R) (S), (S), (S) (S), (R), (R) (R), (S), (S) (R), (S), (R) (S), (R), (S) (R), (R), (S) (S), (S), (R) 8 stereoisomers For any compound, the maximum number of stereoisomers is 2 n where n is the number of stereocenters.

Multiple Stereocenters ow many stereoisomers for 3,4-dimethylhexane???-3,4-dimethylhexane??-3,4-dimethylhexane (3S,4S)-3,4-dimethylhexane (3R,4R)-3,4-dimethylhexane The same compound! (superimposable) enantiomers

so Compounds 3,4-dimethylhexane has 3 stereoisomers! meso-3,4-dimethylhexane meso-3,4-dimethylhexane (3S,4S)-3,4-dimethylhexane (3R,4R)-3,4-dimethylhexane A so Compound (achiral) Enantiomers (chiral)

so Compounds The best way to identify a meso compound is to prove that it is superimposable with its mirror image. owever, a quick test is to see if it contains a plane of symmetry: plane of symmetry meso-3,4-dimethylhexane (3S,4S)-3,4-dimethylhexane (3R,4R)-3,4-dimethylhexane Compounds containing a plane of symmetry are achiral! No plane of symmetry

The Isomers of C 3 4 2, Revisited C 3 C 3 C 2

The Isomers of C 3 4 2, Revisited C 3 C 3 C 2

Racemic Mixtures 3 C C 3 Br addition reaction 3 C Br C 3 But do we get (R) or (S)? (E)-2-butene 2-bromobutane achiral chiral We get both! 3 C C 3 3 C C 3 Br Br 50% (S)-2-bromobutane 50% (R)-2-bromobutane A 50:50 mixture of 2 enantiomers is called a racemic mixture or a racemate.

Racemic Mixtures In dicine C 3 C 3 C 3 C 3 C 3 C 3 (S)-ibuprofen (active) (R)-ibuprofen (inactive) N N N N (R)-Thalidomide (analgesic) (S)-Thalidomide (teratogenic) Prescribed worldwide from 1957-1961 for morning sickness and as a sleep aid

ptical Rotation and Polarimetry randomly oriented light No light emitted monochromatic light source optical polarizer - only allows "horizontal" light to pass through optical polarizer - only allows "vertical" light to pass through Chiral molecules will rotate polarized light: randomly oriented light chiral material detector monochromatic light source optical polarizer - only allows "vertical" light to pass through optical polarizer - only allows "horizontal" light to pass through

ptical Rotation and Polarimetry randomly oriented light chiral material detector monochromatic light source optical polarizer - only allows "vertical" light to pass through optical polarizer - only allows "horizontal" light to pass through The maximum signal will be optained if the second polarizer is rotated to match the light rotation: randomly oriented light chiral material detector maximum signal monochromatic light source optical polarizer optical polarizer - only allows "vertical" light to pass through

ptical Rotation and Polarimetry randomly oriented light chiral material detector maximum signal monochromatic light source optical polarizer optical polarizer - only allows "vertical" light to pass through The amount (in degrees) that a chiral material will rotate light is called the optical rotation. Different chiral molecules will have optical rotations that vary in direction and size of the optical rotation. Enantiomers will always have equal optical rotations but in opposite directions. The optical purity of a substance can be measured by comparing the optical rotation of the sample to the known optical rotation of a single entantiomer of that compound. ptical purity is usually reported in percent entantiomeric excess (%ee). %ee = sample rotation single enantiomer rotation X 100 Enantiomeric excess is the % of the sample that is non-racemic. For example, 80% ee means that there is 90% of one enantiomer and 10% of the other.

Vocabulary (R) or (S): identifies the configuration of a stereocenter using the CIP priority system d- or (+): indicates that a (chiral) compound rotates light in a clockwise direction (this has no correlation with S or R) l or (-): indicates that a (chiral) compound rotates light in a counterclockwise direction (this has no correlation with S or R) dl or (+/-) or rac-: indicates a racemate

Resolution of Enantiomers mixture of 2 diastereomers (R)-compound X react or somehow associate with: (R)-compound X (R)-compound Y (S)-compound X (R)-compound Y (S)-compound X (R)-compound Y racemic mixture of enantiomers Single enantiomer Separate by some technique (chromatography, crystallization, distillation, etc.) (S)-compound X (R)-compound Y (R)-compound X (R)-compound Y single diastereomer somehow remove compound Y single diastereomer (S)-compound X single enantiomer (R)-compound X single enantiomer

Resolution of Enantiomers this nitrogen lone pair is basic (R)-!-methylbenzylamine (S)-2-chloroproprionic acid this hydrogen is acidic 2 N 3 N (R)-2-chloroproprionic acid this hydrogen is acidic this nitrogen lone pair is basic 2 N (R)-!-methylbenzylamine The R,S-diastereomer of the salt 3 N separate The R,R-diastereomer of the salt (R)-2-chloroproprionic acid acidify 3 N 3 N acidify (S)-2-chloroproprionic acid

Chirality Without Stereocenters There is hindered rotation around this bond! N 2 2 N mirror plane 2 N mirror plane N 2 mirror plane

Chirality Without Stereocenters C Why is 1,3-dimethylallane (1,3-dimethyl-2,3-pentadiene) chiral?

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