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JUN- DEC- JUN- DEC- JUN- DEC- JUN- DEC- JUN- DEC- JUN-
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CSIR-NET CHEMICAL SCIENCES | Principles of stereochemistry

Principles of stereochemistry: Configurational and conformational isomerism in acyclic and cyclic

compounds; stereogenicity, stereoselectivity, enantioselectivity, diastereoselectivity and asymmetric
induction

1.In the following compound, the stereo-chemical descriptor for Ha and Hb is…..

(1) enantiotopic

(2) diastereotopic

(3) homotopic

(4) constitutionally heterotopic

Ans (2)

Soln: The Ha and Hb in the compound is diastereotopic faces because they do not superimposes to each
other and not a mirror image when substituted by ‘X’ as shown below,

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Structure ‘A’ and ‘B’ are non super imposable and not a mirror image, so they are diastereomers

2. The correct statements about conformations X and Y of 2-butanone are

1. X is more stable than Y

2. Y is more stable than X
3. Methyl groups in X are anti
4. Methyl groups in Y are gauche

(1) A and D

(2) A and C

(3) B and C

(4) A, C and D

Ans (4)

Soln:

Conformation X & Y are as follows

Statement: A. ‘X’ is more stable than ‘Y’ is correct because methyl groups in ‘X’ are anti

1. ‘Y’ is more stable than ‘X’ is incorrect statement

2. Methyl group in ‘X’ are anti is correct statement
3. Methyl groups in ‘Y’ are gauche is correct statement

So, statement ‘A’, ‘C’ & ‘D’ are correct for structure ‘X’ & ‘Y’

3.The correct order of the magnitude of ‘A values’ for the given substituents in cyclohexane
derivatives is

(1) Ph> CN > Me

(2) Me >Ph>CN
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(3) CN > Me >Ph

(4) Ph> Me > CN

Ans (4)

Soln:

In the following conformations

4.The major product formed in the following reaction sequence is

Ans (1)

Soln:

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5.The correct structure of the intermediate, which leads to the product in the following reaction, is

Ans (1)

Soln: The structure of intermediate in the following reaction is clear from the Mechanism

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6.The major product formed in the following reaction is

Ans (3)

Soln:

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7.The major products A and B in the following reactions are

Ans (3)

8.The major product A and B in the following reaction sequence are

Ans (2)

Soln:

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This is an example of Wolf-Kishner reduction

Reference : Organic Mechanisms Reactions, Stereochemistry and Synthesis , Reinhard Bruckner

9.The major product of the following reaction is

Ans (3)

Soln:

This is an example of chelation control Felkin-Ahn model

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10.The major product formed in the following reaction is

Ans (4)

Soln: This is an example of pinacol-pinacolone cyclization

Subjection of ketal1 to a Lewis acid gives the corresponding oxacarbenium2, which is poised to undergo
a Prins cyclization to furnish intermediate 3. The empty p orbital in 3 (at C10) is aligned periplanar to the
C1-C2 bond thus allowing this bond to migrate to form bicyclic ketone bearing a quaternary center at
C10.

Heating dimethylmenthyl amine oxide gave a mixture of 2- and 3–menthene, whereas isomeric neo
menthylamine oxide gave only 2–menthene. This is an example of pyrolyticsyn elimination

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11.Identify two enantiomers among the following compounds.

(1.) A and B

(2.) A and C

(3.) B and D

(4.) C and D

Ans (4)

Soln:

A and B are homomers ; A and C are diastereomers

B and D are diastereomers ; C and D are enantiomer

12.The configurations of carbon atoms C3 and C4 in D–ribose, respectively, are

(a) R and S

(b) S and R

(c) R and R

(d) S and S

Ans (c)

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Soln:

3.In the most stable conformation of neomenthol, stereochemicalorientation of the three

substituents on thecyclohexane ring are

(a) OH : equatorial; i-Pr : equatorial and Me : equatorial

(b) OH : axial; i-Pr : equatorial and Me : equatorial

(c) OH : equatorial; i-Pr : equatorial and Me : axial

(d) OH : equatorial; i-Pr : axial and Me : equatorial

Ans (b)

Soln:

Neo menthol is represented by ,

Among OH , Me and i-Pr the ‘A’ value of i-Pr is maximum hence it preferentially occupies equatorial
position.

14.The absolute configuration of the two stereogenic (chiral) centres in the following molecule is

(a) 5R, 6R
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(b) 5R, 6S

(c) 5S 6R

(d) 5S, 6S

Ans (c)

Soln:

15.The correct statement about the following molecule is

(a) Molecular is chiral and possesses a chiral plane

(b) Molecule is chiral and possesses a chiral axis.

(c) Molecule is achiral as it possesses a plane of symmetry.

(d) Molecule is achiral as it possesses a centre of symmetry.

Ans (a)

Soln: In Biphenyl system chirality is due to presence of plane that is why it comes under planar
chirality.Since, the given molecule possesses a chiral plane. Thus it is optically active.

16.Consider the following statements about cis- and trans-decalins

(A) cis-isomer is more stable than trans-isomer

(B) trans-isomer is more stable than cis-isomer

(C) trans-isomer undergoes ring-flip

(D) cis-isomer undergoes ring-flip

The correct statements among the above are

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(a) B and D

(b) A and C

(c) A and D

(d) B and C

Ans (a)

Soln:

 Trans-Decalin is more stable about 2.7 kcal/moles as compared with cis-decalin.

 Trans-Decalin has a unique and rigid conformation ring fliping is not possible as it would
otherwise afford a highly strained system with one ring attached to other by two axial bond.
 Cis-Decalin exists as equilibrium between two enantiomeric all chair conformation. So, flip into
one other.

17.The major product formed in the following reaction is

Ans (a)

Soln: In the presence of acid, protonation takes place, thus reaction will proceed via SN 1 mechanism.

Thus, retenation of configuration will be observed and hence the product formed will be

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18.Consider the statements about the following structures X and Y

(A) X andy are resonance structures

(B) X and Y are tautomers

(C) Y is more basic than X

(D) X is more basic than Y

The correct statement(s) among the above is/are

(a) A and C

(b) C

(c) B and D

(d) B and C

Ans (d)

Soln:

Thus, X and Y are tautomers.

Also, it is clear from the structure of X and Y that X is more basic than Y.

19.The constituent amino acids present in the following dipeptide, respectively, are

(a) (R)-aspartic acid and (S)-lysine

(b) (S)-aspartic acid and (R)-lysine

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(c) (R)-glutamic acid and (S)-arginine

(d) (S)-glutamic and (S)-arginine

Ans (a)

Soln:

20.For acylation with acetic anhydride/triethylamine, and oxidation with chromium trioxide of the
trans-and cis-alcohols A and B, the correct statement is

(a) A undergoes acylation as well as oxidation faster than B

(b) B undergoes acylation as well as oxidation faster than A

(c) A undergoes acylation faster than B, whereas B undergoes oxidation faster than A.

(d) B undergoes acylation faster than A, whereas A undergoes oxidation faster than B.

Ans (c)

Soln:

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‘A’ undergoes acylation faster while as ‘B’ undergoes oxidation faster.

21.The two benzylichydrogens HA and HB in the compounds I and II, are

(a) diastereotopic in I and enantiotopic in II

(b) diastereotopic in II and enantiotopic in I

(c) diastereotopic in both I and II

(d) enantiotopic in both I and II

Ans (b)

Soln:

CASE I : The chemically environment of HA and HB are same

CASE II: The chemically environment of HA and HB are different

22.The major product formed in the following reaction sequence is

Ans (b)
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Soln:

23.In the compound given below, the hydrogenes marked A and B are

(a) homotopic

(b) isotopic

(c) enantiotopic

(d) diastereotopic

Ans (c)

Soln: Homomorphic ligands: Ligands are called homomorphic, if they are indistinguishable when
considered in isolation. Here HA and HB are thus homomorphic.

Two homomorphic ligands are homotopic, if substitution of first one and then the other by an atom or a
group, which is not already attached to the ligating centre, gives identical product, else hetertotopic.
Since substitution of HA and HB by D gives different products, thus HA and HB are heterotopic

Also, two heterotopic ligands are enantiotopic if replacement of first one and then the other by a
different achiral ligand gives rise to two enantiomers.
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24.The gauche conformation (Ф=60º) of n-butane posseses

(a) plane of symmmetry; and is achiral

(b) C2-axis of symmetry; and is chiral

(c) centre of symmetry; and is achiral

(d) plane of symmetry; and is chiral

Ans (b)

Soln: The Gauche conformations of n-Butane are non-superimposable mirror image of each other, thus
Gauche conformation is chiral.

If contains neither plane nor centre of symmetry. A C2 axis passes through the mid-point of C2–C3 bond
and bisecting the dihedral angle between the two methyls

25.Among the following, the most suitable reagent for carrying out resolution of racemic 3-
methylcyclohexanone is

Ans (c)

Soln:

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26.The most stable conformations of 1, 2-difluoroethane and dl-2, 3-butanediol are

Ans (d)

Soln:

In general staggered conformation is stable but in case of F- CH2 -CH2 -F Gauche conforamtion is stable
due to Gauche effect i.e. hyper conjugation.

27.The absolute configuration at the two chiralcentres of (–)–camphore is:

(1) 1R, 4R

(b) 1R, 4S

(c) 1S, 4R

(d) 1S, 4S

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Ans (a)

Soln:

CIP Priorities

28.In the compound give below, the relation between H A,HB; and between Br1, Br2 is:

(a) HA, HB are enantiotropic; and Br1, Br2 are diastereotopic

(b) HA, HB are diastereotopic; and Br1, Br2 are enantiotropic

(c) HA, HB are diastereotopic; and Br1, Br2 are homotopic

(d) HA, HB are enantiotropic; and Br1, Br2 are homotopic

Ans (b)

Soln:

Molecule has a plane of symmetry bisecting HA and HB reflecting Br1/Br2 and CH3/CH3.

 Br1 and Br2 are reflected by plane so they are enantiotopic to each other.
 HA and HB are bisecting by plane. Hence, they are diesterotopic to each other.

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29.Given the energy of each gauche butane interaction is 0.9 kcal/mol, G value of the following
reaction is

(a) 0.9 kcal/mol

(b) 1.8 kcal/mol

(c) 2.7 kcal/mol

(d) 3.6 kcal/mol

Ans (b)

Soln:

One 1, 3 interaction energy is 0.9 kcal/mol. So, Total energy 2×0.9 = 1.8 kcal/mol

30.The major product formed in the following reaction sequence is

Ans (c)

Soln:

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31.The structure of meso-tricarboxylic acid that is formed on potassium permanganate oxidation of
abietic acid is:

Ans(b)

Soln:

The molecule have plane of symmetry and opposite discriptor at the chiral centre. So, it is an example of
meso compound.

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32.The major product formed in the following reaction is:

Ans(d)

Soln:

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33.For the following two reactions A and B, the correct statement is:

Ans(b)

Soln:

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34.The configuration at the two stereocentres in the compound given below are

(a) 1R, 4R

(b) 1R, 4S

(c) 1S, 4R

(d) 1S, 4S

Ans (a)

35.The two compounds given below are

(a) Enantiomers

(b) Identical

(c) Diastereomers

(d) Regioisomers.

Ans (b)

36.In the most stable conformation of trans-1-t-butyl-3-methylcyclohexane, the substituents at C–1

and C–3, respectively, are

(a) Axial and equatorial

(b) Equatorial and equatorial

(c) Equatorial and axial

(d) Axial and axial.

Ans (c)

37.The relative rates of solvolysis of iodides A-C are

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(a) C > A > B

(b) C > B > A

(c) B > C > A

(d) B > A > C

Ans (a)

38.The major product formed in the following reaction is:

Ans (b)

39.The gauche interaction values for Me/Me, Me/Br and Br/Br are 3.3, 0.8 and 3.0 kJ/mol,
respectively. Among the following, the most stable conformation of 2, 3-dibromobutane is:

Ans (b)

Soln:

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40.Among A-C, the compounds which can exhibit optical activity are

(a) A, B and C

(b) A and B only

(c) A and C only

(d) B and C only

Ans (c)

41.In the following Markonikov addition reaction, the products A and B are

(a) homomers

(b) enantiomers

(c) diastereomers

(d) regioisomers

Ans (c)

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