1 Biologically-active Chiral Molecules HO HO OH HO O O O OH - - PDF document

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1 Biologically-active Chiral Molecules HO HO OH HO O O O OH - - PDF document

Chapter 7 - Stereochemistry Enantiomers of bromochlorofluoromethane Non-superimposable mirror images Enantiomers YSU YSU Biologically-active Chiral Molecules YSU YSU 1 Biologically-active Chiral Molecules HO HO OH HO O O O OH


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Chapter 7 - Stereochemistry

Enantiomers of bromochlorofluoromethane

Non-superimposable mirror images – Enantiomers

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Biologically-active Chiral Molecules

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Biologically-active Chiral Molecules

HO H H H cholesterol NH2 HO HO L-dopa OH OH HO O HO O OH OH HO HO O sucrose

$100 billion sales worldwide in 2000 Account for 32% of the $360 billion total drug sales

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The Chirality Centre - Stereoisomerism

Carbon atom here is asymmetric C is a stereogenic center

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7.3 Symmetry in Achiral Structures

Mirror images of chlorodifluoromethane are superimposable Figure 7.2

Achiral i.e. not chiral

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Typical polarimeter setup : []D = 100 x (rotation)/(cell length) x (concentration)

7.4 Measurement of Optical Activity

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7.8 Enantiomers

  • same physical properties except rotation of plane polarized light
  • one enantiomer positive rotation (+) other negative rotation (‐)
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Which molecules contain chiral (stereogenic) centers?

The stereogenic C must have 4 different groups attached

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7.5 Absolute and Relative Configuration

Absolute Configuration – Actual arrangement of substituents in space (+)‐2‐butanol and (‐)‐2‐butanol, but which is which? Relative Configuration ‐ Configuration relative to another compound. Pre‐1951, compounds could be related to each other but the absolute configuration was not able to be determined.

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7.6 Nomenclature - Use of the Cahn-Ingold-Prelog System

S enantiomer R enantiomer R ‐ Rectus ‐ the clockwise arrangement of groups S ‐ Sinestre ‐ the counterclockwise arrangement of groups

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7.6 Nomenclature - Use of the Cahn-Ingold-Prelog System

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7.7 Fischer Projection Formulas

Figure 7.5

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7.9 Reactions that create a Chirality Center

Figure 7.6

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7.10 Chiral molecules with two Chirality Centers

Figure 7.7

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7.10 Representations of (2R, 3R)-dihydroxybutanoic acid

All the same molecule: (a) and (b) differ only by bond rotation (b) leads to correct Fischer projection

Conversion of “zig‐zag” picture to Fischer projection

Figure 7.8

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7.10 Chiral molecules with two Chirality Centers

Important stereochemical labels later, particularly in carbohydrate (sugar) chemistry and biochemistry

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7.10 Chiral molecules with two Chirality Centers

Applies to other cycles, including cyclohexane; increases the molecular diversity possible using simple structures

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7.11 Achiral molecules with two Chirality Centers

Figure 7.9

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Meso-2,3-butanediol

Figure 7.10

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7.11 Stereogenic Centers in Cholic Acid

Figure 7.11

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7.13 Reactions that produce diastereomers

Figure 7.12

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7.13 Reactions that produce diastereomers

Figure 7.12

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7.14 Resolution of a chiral substance into its enantiomers

Figure 7.13

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Not covering 7.15 and 7.16