CHM 1321 Assignment 3 - ANSWERS

1) Identify each of the following pairs as constitutional isomers, stereoisomers (configurational isomers), or conformers.
a) + Stereoisomers b) + Constitutional isomers c) + Same compound f) Br Br + Br e) Br Br + Br d) Br Br + Br Stereoisomers Br

Br

Constitutional isomers Br

conformers (conf ormational isomers)

2) Draw each structure below along with its mirror image. Indicate whether the compound is chiral or achiral. a) cis-1,2-dimethylcyclopentane. b) trans-1,2-dimethylcyclopentane
a) CH3 CH3 H3C H3C b) CH3 CH3 H3C H3C

Achiral - mirror images are superimposable plane of symmetry exists (meso compound)

Chiral - mirror images are not superimposable

c) cis-1,3-dimethylcyclohexane d) trans-1,3-dimethylcyclohexane
CH3 c) H3C d) CH3 H3C

CH3 CH3 CH3 CH3 Achiral - mirror images are superimposable Chiral - mirror images are not superimposable plane of symmetry exists (meso compound) O O O O

e)

f)

Achiral - mirror images are superimposable - no stereogenic centre, 2 identical groups on tetrasubstituted carbon Plane of symmetry exists

Chiral - mirror images are not superimposable

Assignment 3 - Answers Question 2 contd: g) CH3CClBrH h) (CH3)2CHOH

g) Br Cl Cl Br

i) CH3CH2CHOHCH3
h) OH

j)CH3CH2CHOHCH2CH3
HO

Chiral - mirror images not superimposable i) OH OH j)

Achiral - mirror images superimposable (2 identical groups on central carbon)

OH

OH

Chiral - mirror images not superimposable

Achiral - mirror images superimposable (2 identical groups on central carbon) Plane of symmetry exists

3) Identify the chiral centres in the following molecules: (indicated with a *) a. fexofenadine (Allegra):
CO2 H N OH

*
OH

b.

Indinavir (Crixivan):
N N O N OH OH

*
N H

*
C(CH3 )3

*
O

H N

Assignment 3 - Answers 4) Draw each of the following compounds in three dimensions. Draw the mirror image of each and determine whether the compounds are chiral. For all chiral compounds, determine whether the configuration of each stereogenic centre is R or S. a) 1,3-dibromobutane b) 2-butanol c) 2-methylpentane d) 3-methylpentane e) 3-methylhexane f) 1,2-dihydroxypropane g) 1, 2, 4-trihydroxybutane
(Priorities in red) Br
2 4H 1 R 3 3 S 2 2 3 3 4H 2

a)

Br

b)

c)
1

Br

Br Chiral

4H

4H OH 1

OH Achiral
4H 1 1

Chiral

4H

3 S

4H 3 2 R

OH
R

H OH OH HO
S 2 3

d) Achiral
4 1OH

e)
1

f)
1 3

Chiral

Chiral

H OH
S 3

g) HO

OH HO
2

Chiral

OH

5) For the following compounds, show the stereogenic center(s) by labeling them with a star (*) and determine the configuration of each centre (R or S).
Priorities in red
4 1 1

H *
R

Cl HO
2

CH3

b)

2 S 1

Br R H * CH2CH3 H3C
4 3 2 2

S 2

c)

Cl

*
4H 1OH

Br

d)

2 4H 3

S 1

*
4

H H H
2 3

Br * H4
3 1

CHO S f) 3 * CHCH 2 (CH3O)2HC CH(CH3)2 1

4

O g)
3 4H 1 R 2

h)

CO2H * (back) H R

*S
3 R

O * OR
2 3

i)

j) H C S 3 1 3 * H4

O O

k)
S

* * *

l)
R

OH

* CH3
4

NH2

3 4H R 2 R

*
3 S

* * OH H4
1 2

* *

*
2

* OH H 1
4

OH

Assignment 3 - Answers 6) Phenylalanine has the following structure, given that the configuration is S, what is the proper way to draw the compound?
One way to approach this problem is to draw the chiral center in your favourite conformation (arbitrary) and assign R or S to it. If you've drawn the S conformer, you've answered the question. If not, switch any two groups to obtain the opposite conformer.

H2N O

OH

S H2N O

OH

7) Assign the configuration at each stereogenic centre. Convert the following to Fischer projections.
Br a) H HO
2

CH 3 Br
1 S

b)

H H3 C
2 3 1

c)

Cl Cl
3 4

OH

d)

HO
4H

CH 3
3

H 3C
4H

Ph
S

CH2 OH H Cl 1 S CH2 Cl
2

H3 C
3 2

1 S

Ph =

OH H e) O O CHCH 2 CH(CH 3 )2 O 1 O
4H S 3 2

OH CHO g) H 2N O
2 3 R

f ) HO OH

h) OH HO

OH OH OH
2

OH

O CO2 H OH 3 H
4 2

CHO HO H S HO HO HO HS HS H S OH

CO 2H H4 NH 2
1

CO 2H H OH 1 H CO 2H
3

HO

H R HO
1

CO2 H

Br i) H H CH 3 CH 2CH3 Cl OH priorities
3 3

CH3 H H H H Br S Br R

CH 2CH3 Cl HR HO HS CH 3

j)

Br H3 C

priorities
1

CH 2CH3 Cl HR 4 2 HO H CH 3
1

Cl HO
1

CH 2CH3 H HS
4

CH 3

H S Br H 2 Br

CH 3 H Br
2 4H 3 R

Br 1

CH 3

Assignment 3 - Answers 8) Convert the following to zig-zag structures (line structures). Assign the configuration at each stereogenic centre.
a) COOH HO H CH3 OH OH S O S O b) COOH H CH3 NH2 NH2 OH c) CH2CH2OH H Br CH3 Br R OH R H d) H CH2OH Cl Br CH3 Br S Cl OH

e)

CH2OH H OH H OH CH3 OH R S OH OH

f)

H Br

CH2OH OH OH CH3

g)

HO Br S S OH OH

H HO H H

CHO OH H OH OH OH

H3CS H CH3CONH O

h)

H SCH3 OH H CH3 NH S R OH S S

HO

OH OH R CHO S R R OH OH

9) Give the stereochemical relationship between each pair of isomers (enantiomers, diastereomers, meso compounds). USE A MODEL!
a) CH3 H OH H OH CH3 CH3 HO H HO H CH3 CH2 OH CH 2OH H OH HO H b) H HO H OH CH 3 CH3 Enantiomers c) CH 3 Br H Cl Br Cl H CH3

Meso Compound

Same Compound

OH d) OH Enantiomers Cl f) g) H diastereomers C HO OH e) HO N

OH N

Same Compound Br C H H Cl h) Br Br Br enantiomers

CH 3 H

H 3C

enantiomers

10) Which of the following pairs of compounds could be separated by a method such as distillation or recrystallization? a. Diastereomers separable b. Enantiomers not separable c. Diastereomers separable 5