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MW CH402 questions and answers from 2010 paper:
1
Looking for; (i) protonation of an enolate, (ii) alkylation of an enolate
with BnBr, (iii) ring opening cyclohexene oxide with BnMgBr then oxidation
or (iv) any other suitable method. One mark each.
[10%]
(b) The heterocyclic compound 2 can be used to catalyse the addition of PhCH2Br to 3
to give the enantiomerically enriched product 4.
10 mol%
Ph Ph
O O Ph
N H
H
2
PhCH2Br 96% ee
3 4
(ii) Explain, with the aid of appropriate illustrations, how the catalyst
subsequently controls the absolute configuration of the product.
[15%]
The upper face is blocked and
Ph Ph Ph Ph alkylation goes on lower face
N N O
H Ph H Ph
Br
Ph hydrolysis
10 mol%
O Ph Ph O
N
H 50% ee
2
Ph
Ph2CuLi
5 6 H
[10%]
In this case a similar intermediate forms as in (ii) however the CH2Ph group is further from
the centre to which the Ph- adds hence it exerts less control. 2 marks.
NaIO4
7 8
Given this information;
OH
F3C F3C
9 10
OH
O OH
OH
OH
AD oxidation Wittig
(ii) Devise a synthesis of ester 12 from alkene 11. Reagents should be given for
each step, but mechanisms need not be illustrated.
O
Ph O
Me
H
O O
O O
11 12
O O
HO Ph O Ph O
OH OH Me
H
O PhCOCl i) OH to OTs
AD O O with TsCl. O
O O ii) Me2CuLi
O O
11 12
One mark per step above.
[15%]
(i) Illustrate how the phenyl rings in 13 create a chiral environment around the
rhodium(I) atom.
2 marks.
[10%]
(ii) Illustrate the two diastereoisomers which are formed upon co-ordination of
substrate 14 to complex 13.
Ph
O Ph
P Rh P O
P Rh P
Me N CO2H
H HO2C N Me
H
(iii) Explain how the catalyst thus achieves a selective hydrogenation of 14.
The diastereoisomers are of different energies (1 mark) and therefore of
different relative abundances (1 mark) and different reactivities (1 mark).
The hydrogen gas first goes onto the Rh and is transferred preferentially to
the proximal face of the alkene in the more reactive (but less abundant)
complex (1 mark) which is presumably the left hand one above.
[20%]
(iv) Devise a synthetic sequence for the synthesis of the α-arylpropionic acid 15
from methyl ester 16, using complex 13 in a hydrogenation step. Reagents
should be given, but mechanisms need not be illustrated.
Me H
MeO HO
O O
16 15
MeO MeO HO
CH2O, Me2NH hydrolysis
O O O
16
The acid group in the hydrogenation Asymmetric hydrogenation
substrate co-ordinates to Rh(I) in an using 13.
analogous mode to 14, thus directing Me H
the reaction. HO
One mark per step and one for explanation.
O
15
[20%]
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CH402
2006-2007
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