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9. Stereochemistry

9. Stereochemistry. Based on McMurry’s Organic Chemistry , 7 th edition. Stereochemistry. Some objects are not the same as their mirror images (they have no plane of symmetry) A right-hand glove is different than a left-hand glove (See Figure 9.1)

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9. Stereochemistry

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  1. 9. Stereochemistry Based on McMurry’s Organic Chemistry, 7th edition

  2. Stereochemistry • Some objects are not the same as their mirror images (they have no plane of symmetry) • A right-hand glove is different than a left-hand glove (See Figure 9.1) • The property is commonly called “handedness” • Many organic molecules (including most biochemical compounds) have handedness that results from substitution patterns on sp3 hybridized carbon

  3. Enantiomers – Mirror Images • Molecules exist as three-dimensional objects • Some molecules are the same as their mirror image • Some molecules are different than their mirror image • These are stereoisomers called enantiomers

  4. 9.1 Enantiomers and the Tetrahedral Carbon • Enantiomers are molecules that are not the same as their mirror image • They are the “same” if the positions of the atoms can coincide on a one-to-one basis (we test if they are superimposable, which is imaginary) • This is illustrated by enantiomers of lactic acid

  5. Examples of Enantiomers • Molecules that have one carbon with 4 different substituents have a nonsuperimposable mirror image – enantiomer

  6. Mirror-image Forms of Lactic Acid • When H andOH substituents match up, COOHand CH3don’t • when COOH and CH3coincide, Hand OH don’t

  7. 9.2 The Reason for Handedness: Chirality • Molecules that are not superimposable with their mirror images are chiral (have handedness) • A plane of symmetry divides an entire molecule into two pieces that are exact mirror images • A molecule with a plane of symmetry is the same as its mirror image and is said to be achiral (See Figure 9.4 for examples)

  8. Chirality • If an object has a plane of symmetry it is necessarily the same as its mirror image • The lack of a plane of symmetry is called “handedness”, chirality • Hands, gloves are prime examples of chiral object • They have a “left” and a “right” version

  9. The flask has a mirror plane, or plane of symmetry There is no mirror plane for a hand

  10. Chirality Centers • A point in a molecule where four different groups (or atoms) are attached to carbon is called a chirality center • There are two nonsuperimposable ways that 4 different different groups (or atoms) can be attached to one carbon atom • If two groups are the same, then there is only one way • A chiral molecule usually has at least one chirality center

  11. Chirality Centers in Chiral Molecules • Groups are considered “different” if there is any structural variation (if the groups could not be superimposed if detached, they are different) • In cyclic molecules, we compare by following in each direction in a ring

  12. Problem 9.2: Chirality Centers?

  13. Solution:

  14. 9.3 Optical Activity • Light restricted to pass through a plane is plane-polarized • Plane-polarized light that passes through solutions of achiral compounds remains in that plane • Solutions of chiral compounds rotate plane-polarized light and the molecules are said to be optically active • Phenomenon discovered by Biot in the early 19th century

  15. Optical Activity • Light passes through a plane polarizer • Plane polarized light is rotated in solutions of optically active compounds • Measured with polarimeter • Rotation, in degrees, is [] • Clockwise rotation is called dextrorotatory • Anti-clockwise is levorotatory

  16. Measurement of Optical Rotation • A polarimeter measures the rotation of plane-polarized that has passed through a solution • The source passes through a polarizer, and then is detected at a second polarizer • The angle between the entrance and exit planes is the optical rotation.

  17. Polarimeter (schematic)

  18. A Simple Polarimeter • Measures extent of rotation of plane polarized light • Operator lines up polarizing analyzer and measures angle between incoming and outgoing light

  19. Specific Rotation • To have a basis for comparison, define specific rotation, []D for an optically active compound • []D = observed rotation/(pathlength x concentration) = /(l x C) = degrees/(dm x g/mL) • Specific rotation is that observed for 1 g/mL in solution in cell with a 10 cm path using light from sodium metal vapor (589 nanometers)

  20. Characteristic property of a compound that is optically active – the compound must be chiral The specific rotation of the enantiomer is equal in magnitude but opposite in sign (or direction). Specific Rotation and Molecules

  21. 9.4 Pasteur’s Discovery of Enantiomers (1849) • Louis Pasteur discovered that sodium ammonium salts of tartaric acid crystallize into right handed and left handed forms • The optical rotations of equal concentrations of these forms have opposite optical rotations • The solutions contain mirror image isomers, called enantiomers and they crystallized in distinctly different shapes – such an event is rare

  22. Relative 3-Dimensionl Structure • The original method was a correlation system, classifying related molecules into “families” based on carbohydrates • Correlate to D- and L-glyceraldehyde • D-erythrose is the mirror image of L-erythrose • This does not apply in general

  23. 9.5 Sequence Rules for Specification of Configuration • A general method applies to the configuration at each chirality center (instead of to the the whole molecule) • The configuration is specified by the relative positions of all the groups with respect to each other at the chirality center • The groups are ranked in an established priority sequence (the same as the one used to determine E or Z)and compared. • The relationship of the groups in priority order in space determines the label applied to the configuration, according to a rule

  24. Sequence Rules (IUPAC) • Assign each group priority according to the Cahn-Ingold-Prelog scheme With the lowest priority group pointing away, look at remaining 3 groups in a plane • Clockwise is designated R (from Latin for “right”) • Counterclockwise is designated S (from Latin word for “left”)

  25. Configuration at Chirality Center • Lowest priority group is pointed away and direction of higher 3 is clockwise, or right turn

  26. Examples of Applying Sequence Rules

  27. Practice Problem 9.4

  28. Problem 9.9: Assign R or S

  29. Problem 9.44: R or S?

  30. Solution:

  31. Problem 9.50: Same structure or enantiomers?

  32. 2S,3S 2R,3R 2R,3S 2S,3R 9.6 Diastereomers • Molecules with more than one chirality center have mirror image stereoisomers that are enantiomers • In addition they can have stereoisomeric forms that are not mirror images, called diastereomers • See Figure 9-10

  33. Problem 9.45: R or S?

  34. Epimers: diastereomers that differ at only one chiral center

  35. Problem 9.13: Assign R or S

  36. Tartaric acid: Enantiomers What are they?

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