CH2202 Outline Answers 2007/8 – Autumn Exam

1.
CO2H
Me CO2H
H OH
HO2C Me Me Me
Me
1 2
a) 1 (unseen, seen related) 3 (one meso) [1]; appropriate diagram showing meso [1]
b) 2 R (unseen, seen related) [1], assignment of groups/working [1]
c) (unseen, seen related) appropriate chair diagram with clear indication of eq t-Bu [1]

2.
i) (unseen) All identical structures (meso) [3]
ii) (unseen, seen related) diastereomers [2]

3. The main point which is expected here is the different between pentadienyl and
cyclopentadienyl anions, methyl and 2-pentyl anions and the stabilisation of an anion by a
carbonyl.

4. The reaction mechanism is expected, with correct protonation/deprotonation and bond

forming/breaking steps.

5.
a) chiral = non-sup mirror image (lectures) [1], (unseen, seen related) 6 chiral , non-isolable [1];
7 chiral, isolable in optically pure form [1]; 8 and 9 both achiral [2]
b) 10 achiral (unseen), 11 chiral (unseen), 12 chiral (lectures), 13 chiral (lectures). For each [0.5]
for answer, [1] for explanation. A good answer will depict object and mirror image and show
they are non-superimposable.
c) 14 (unseen, seen related) well drawn chair conformation with ax & eq groups [1] eq CO2H
groups [1] achiral [1]
d) (all unseen) Each answer [1] should be accompanied with a suitable explanation [1]:
i) chiral, racemic; ii) not chiral; iii) chiral, single stereoisomer/enantiomer

6.
a) (unseen, worked related)
Ph
OBs Me Me H
Ph a or Ph a etc [2]
b Me b OBs
[2] Me H
c Me c Me OBs

b) (unseen, worked related)

c c OAc Me
Me Me
or Me H H OAc etc.
Ph b Ph b etc or
OAc OAc Me H H Ph [2]
a a [2]
Me Me Ph Me
c) (seen related) All four stereoisomers [2], enantiomers shown [1], diastereomers shown [1]
d) SN2 mechanism [1], correctly drawn mechanistically [2], proceeds with inversion [1]
e) (unseen) A good answer might include description of a mechanistic switch over to SN1 via
phenonium ion/anchimeric assistance [1], shown mechanistically [1] proceeding with retention
[1]. Mention should be made of the increased stability of carbocation with mesomeric donation
of the methoxy group [1]. (this part of the question is designed to distinguish between first class
and top first class candidates).

7. (a) The stabilisation of the build-up of negative charge in the SN2 transition state and the
corresponding destabilisation of a carbenium ion is expected.

(b) This reaction should be explained using anchimeric assistance. Since the SN2 reaction takes
place at a different carbon atom in each step, the net result is inversion of the stereogenic centre.

(c) This is a fairly straightforward SNi substitution as seen in lectures. The involvement of a
tight ion pair to explain retention of configuration should be clearly stated.

8. (a) This has been seen in lectures in reverse (given starting material stereochemistry). Credit
will be given for clear diagrams showing stereochemistry. Any appropriate stereochemical
representation can be used.

(b) The importance of a t-butyl group locking the cyclohexane ring needs to be understood, as
does the stereoelectronic requirement of a trans diaxial bromine and hydrogen for elimination to
occur. The third compound has all three substitutents equatorial in its lowest energy conformer,
and will require all three to be axial in order to eliminate. This is therefore the slowest, followed
by the first compound. The second and fourth compounds have axial bromine in their lowest
energy conformer, and therefore eliminate rapidly. The difference here is that the fourth
compound can eliminate in two directions. 3 marks per compound, with credit given for correct
working.

CH2202 Outline Answers 2007/8 – Refer Exam

1. 1 (unseen) chair with equatorial isopropyl group [2], R,S [0.5 each], priorities [0.5 each]
b R c c
CH3 CO2H
c
S a
Cl H OH b
b
R
a Cl OEt
a
1 2

2.
a) Each staggered conformation (anti and gauche) must clearly show stereochemistry [1 each].
Good brief explanation for stability of anti could be made in terms of torsional strain, but Van
der Waals interactions will also be accepted [1]
b) Two chair conformations must show all ax or all eq environments [1]. All eq more stable can
be argued in terms of minimizing 1,3-diaxial interactions [1]

3. The fact that axial leaving groups react faster than equatorial should be recognised. The
second compound has not been seen, but students should realise that the additional methyl group
provides additional steric hindrance, and will therefore react slowest.

4. The reaction mechanism is expected, with correct protonation/deprotonation and bond

forming/breaking steps.

5.
a) Each projection correctly showing stereochemistry [2x1], assignment of priorities [2x1]
a c
Cl O
c b
b O
a

6 7 (unseen, but worked related problems)

b) Any method will be considered on its viability, but would expect routes from alcohols or their
derivatives. Assessment will be based upon choice of precursor [1], reagent [1], ability to access
in optically pure form [1], correct choice of route to access S-stereoisomer [1] (unseen).
c) For each mechanism, expect curly arrow description [2x2] and stereochemical outcome [2x1],
with correct application of this to (S)-6 [1] (lectures).
d) Major mechanism operating is SN1 [1] as product is near racemic [1]. Small amount of
inversion is due to some SN2 or tight ion pair considerations under SN1 [1].
e) Better nucleophile would expect to promote SN2 over SN1 but no change is observed [1].
Hence probable reaction proceeds exclusively by SN1, with some tight ion pair involvement [1].

6. A positive marking scheme will be applied, with credit given for correct and relevant
statements. Stabilisation of cations by alkyl substitution, conjugated double-bonds, aromaticity,
adjacent heteroatom lone pairs, etc. should be discussed, with suitable diagrams to show the
origin of stabilisation (conjugation, hyperconjugation). Detabilisation of cations by adjacent
carbonyl groups should also be mentioned.

7. (seen examples related to all these in lectures). A good answer will include the examples
given and use them to discuss stereoisomerism in meso compounds, allenes, double bond
geometries/cycloalkanes, stereogenic phosphorous & nitrogen inversion and ortho-disubstituted
biphenyls [5x4].

8. (a) The formation of an aromatic anion should be recognised., leading to an E1cb elimination.
The favourable entropic contribution of CO2 evolution should also be mentioned.

(b) Both of these reactions will be covered in lectures. The students should convert the Fischer
projection into either a flying wedge or Newmann projection in order to state the stereochemical
outcome of each reaction. The Wittig reaction should be seen as a syn elimination, with the
driving force (P=O bond formation) appreciated.
(c) Retention of configuration by two sequential inversion reactions.