ISOMERS

(same no. and kinds of atoms, but dif fer in the way the atoms are arranged, dif ferent compounds with the same molecular f ormula )

LMZ/CHEM109A/ Winter 2010

4. Fisher Projections (Sec 5.5) A tetrahedral carbon atom is represented in Fischer projection by two crossed lines. By convention, the horizontal lines represent bonds coming out of the page, and the vertical lines represent bonds going into the page.

Constitutional (or structural) Isomers
(dif f erent connections of atoms; dif f erent bonding sequence) (sec. 2.8)

Stereoisomers
(same connections of atoms but diff erent 3-D arrangement in space)

Same f unctional group, but diff erent carbon skeleton

diff erent f unctional groups

diff erent positions of f unctional group

(Sec. 2.8) geometric isomers ( or cis-trans isomers)

enantiomers (Chap. 5)

e.g. C5H12
CH3 CH2 CH2 CH3 H3C C CH3 CH3 CH2 CH3 H3C HC CH3 CH3 CH2

e.g. C2H6O
H H H C C OH H H H H H

e.g. C3H8O
OH H H H C C C H H H H H OH H C C C H H H H

e.g. A
H

B H
Cl Cl H

A H

H B
Cl H Cl H

diastereomers (Chap. 5)

cis-isomer

trans-isomer

5. Asymmetric center and stereocenters (stereogenic centers) - Asymmetric center: chiral carbon center - stereogenic center: stereoisomers formed when two substituents interchanged.

H C O C H H H

cis-isomer

H

trans-isomer

Chapter 5 Stereochemistry I. Chiral Compounds and Enantiomers (Sec. 5.2-5.3) 1. Molecules that are not superimposable on their mirror images and thus exist in two enantiomeric forms (enantiomers) are said to be chiral.
A D C B mirror images B A D C

2. A molecule is chiral when there is no plane of symmetry in the molecule (i.e. no imaginary plane that can cut through the molecule so that one half of molecule is not the exact mirror image of the other half--- note: the molecule can rotate) 3. A carbon atom bonded to four different groups is called a chiral (asymmetric) center. (NOTE: Molecules that possess chiral carbons are usually chiral. Exception: mesocompound or a compound that have a plane of symmetry) Which of the following compounds are chiral? Identify the meso compound(s).
e.g. 1 CH3 H HOOC H H HOOC e.g. 2 CH3 OH e.g. 3 H CH3 e.g. 4 H CH3 O e.g . 5 Br H Cl Br H Cl

II. Sequence Rules (Cahn-Ingold-Prelog Rules) for Specification of Configuration (Sec. 5.7) - a verbal method for indicating the 3-D arrangement of atoms (the configuration) at the stereogenic (chiral) center 1. Look at the four atoms directly attached to the chiral center, - assign priorities in order of decreasing atomic number e.g.1 , I > Br > Cl > S > F > O > N > C > 3H (T) > 2H (D) > 1H - the group with the highest atomic number is ranked first; the group with the lowest atomic number is ranked fourth Br e.g. 3 e.g. 2 Br
Cl H CH3
H CH3 CH2CH3

2. If a decision about priority can't be reached by applying rule 1, compare atomic numbers of the second atoms in each substituent, - continuing on as necessary through the third or fourth atoms outward until the first point of difference is reached. - one high-priority atom takes priority over any number of lower-priority atoms
e.g. 4 H C Br H H CH3 H H H

>

C Cl Cl

>

C CH3 CH3

>

C CH3 CH3

>

C CH3 H

>

C H H

e.g. 5

CH3 C CH3 CH3

CH2Br

CH2Br

CH3

>

C CH3 H

>

C H H

>

C H H

Multiple-bonded atoms are considered as an equivalent number of single-bonded atoms e. Which of the following compounds is chiral? Br Br cis-1 .compounds? Relationships between A and B: C and D: A and C or D: B and C or D: C. Chiral compounds can rotate the plane polarized light .11) A. 8 HOH2C OHC H OH H COOH 4.13) 2. COOH HOOC Relationships between A and B: C and D: A and C or D: B and C or D: Enantiomers: stereoisomers that are not superimposable on their mirror images. but achiral due to the presence of a symmetry plane IV.optically active 3.12) . Nomenclature (sec. if a curved arrow drawn from the highest to the second-highest to third-highest priority substituent (123) is clockwise. 5. 6 OH C O becomes mirror H COOH OH C C A H OH COOH HO OH COOH H C C H COOH B C H OH C O C N becomes (N) (C) C N (N) (C) COOH OH C C mirror OH COOH H C C H OH COOH D (O) (C) OH e. is not related to the R. (Fig. Molecules with Two or More Chiral (Stereogenic) Centers (Sec.minus sign (-) dextrorotatory compounds: rotate polarized light to the right. 5. 5. diastereomers have the same configuration in at least one center but opposite configurations at the others. Which of the compounds above are meso. its mirror image must have S configuration.the R. we can find the new plane of polarization and the extent of rotation (°) c) levorotatory compounds: rotate polarized light to the left: (observing directly end on at the analyzer) -. B. We consider such a molecule to be achiral.compounds with two or more stereogenic centers.g. (+) or (-). Chirality of Conformationally Mobile Systems A molecule cannot be optically active if its chiral conformations are in equilibrium with their mirror images. 7 HO COOH CH3 H e. S designation. Optical Activity and Racemic Mixtures (Sec.the optical rotation (+) or (-) is determined experimentally i.the configuration of each chiral center is individually determined. 5. In general.8-5. 5. a molecule with n stereogenic centers gives rise to a maximum of 2n stereoisomers (2n-1 pairs of enantiomers). S configuration is designated from the arrangements of groups in space -.12) a) plane-polarized light pass through the solution of optically active compound and the rotation of the plane of the polarized light occurs b) by rotating the analyzer until the light passes through it.LMZ/CHEM109A/ Winter 2010 3. Plane-polarized light: light waves oscillating in a single plane (Fig 5. plus sign (+) NOTE: (i) The sign of optical rotation. . If a molecule has R configuration. Polarimeter . away from us.e.g.10 ) 1. -. Mentally orienting the molecule so that the group of lowest priority (fourth) is pointing directly back. we say that the chiral center has the S configuration.intrusment for measuring the amount of rotation. Diastereomers: stereoisomers that are not identical and are not mirror images of each other. Meso Compounds (Sec.13) .2 -d ib ro m o c y clo h e xa n e Br Br H Br Br Br H H Br H Br H Br H Br H Br Br H III.2 -d ib ro m o cy c lo h e xan e D. (Exception: meso compounds). we say that the chiral center has the R configuration. H COOH NH2 C C H CH3 A H H2N C C HO H CH3 H3C COOH HOOC OH HO CH3 B H C C OH H H3C NH2 H2N C H C C OH H HO H mirror H2N COOH H C C H OH CH3 H COOH NH2 C C H H CH3 D H C C CH3 NH2 mirror H2N COOH H C C OH Br Br Br t r a n s -1 . enantiomers have opposite configuration at all stereogenic centers. A chiral compound of R configuration can be (+) or (-) in optical activity.g. Look at the three remaining substituents. if it is counterclockwise.

2°. VI.compounds with four different groups attached.: c = 1 g/mL . N atom can be asymmetric centers (sec. A 1. 4. specific rotation []D is used path length: l = 1 dm (10 cm). 5. b) The solutions of the crystals of either kind (+) or (-) were optically active.differs in the sign of their rotation of plane-polarized light.g. Diastereomers: different properties 3. sample conc. and therefore depends on the concentration of the sample and the path length (length of sample tube in the direction of light) -. 2. Why? (iii) What about the optical rotation of achiral compounds or meso.e. chemical propertiesexcept for reactions with chiral compounds. Pasteur found that sodium ammonium tartrate formed two distinct kinds of crystals (1849).LMZ/CHEM109A/ Winter 2010 -. e) enantiomeric excess e.17) . Racemic mixture or racemate: . S configuration) will be (? ) in optical activity.acts as a pure compound. but inversion fast (racemization) ~6 kcal/mol VI. = observed specific rotation/specific rotation of the pure enantiomer x 100% V. but solutions of the orginal salt (±). 5. Stereochemistry of alkene reactions a) The two kinds of crystals were different in shapes and nonsuperimposable mirror images of each other. . . its mirror image (enantiomer.5 g sample of compound A was dissolved in 10 mL ethanol and placed in a sample cell with a 5.0 cm path length. The observed rotation at the sodium D line was 1.compounds with a lone electron pair N is a chiral (asymmetric center).if a chiral compound of R configuration is (+) in optical activity.the amount of rotation depends on the number of molecules that the light beam encounters.compounds? d) specific rotation: -. Physical Properties of Stereoismer and Pasteur's Discovery of Enantiomers (Sec.to standardized. (ii) A racemic mixture or racemate (an equal (1:1) mixture of two enantiomers) show zero rotation. Enantiomers: same melting points. Calculate the specific rotation []D for compound A. but their physical properties are different from either of the enantiomers due to different packing and intermolecular interactions. c (g/mL) e. (a 50:50 mixture of each kind) was optically. boiling points. light:  = 598 nm (sodium D line).at 25°C []25D = Observed rotation (degrees)_______ = °/lc path length l (dm) x conc. solubilities. COO H C C OH COO H H COO OH OH C C OH COO H .16) 1.

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