CHEM 30123 – FALL 2016 Name:_________KEY______________

EXAM #3
(150pts: 5 questions, 4 pages, page 4 is blank)
1 (20 pts) Fill in the blanks, specify relative stereochemistry; Suggest a reagent and/or a catalyst
that could induce an equilibrium between A and B, and indicate whether the equilibrium would
be shifted towards A or B..

peroxyacid reacts with alkenes to give epoxides
O
O
O2H

trans is more
stable; hence +
_ A free rotation due
the equilibrium
shift HO to the ring-opened
intermidiate
H H
trans epoxide is
O preferred due to sterics
intermediate
O
O2H

+
_ B H
O
since H + is the only species present at the
arrow, no atoms can be
added/removed to the trans alkene

2 (25 pts) Write a detailed arrow-pushing mechanism for the following transformation:

only can be
an electrophile
O H H
EtO O
OEt
H Cl
O EtO – acts as OEt
a Base, picks O
up the most
acidic H intramolecular
H H SN 2
OEt OEt
Cl Cl
O
O O OEt
Cl
O

1
3 (25pts) The ketoester shown below could be synthesized in 2 steps from 1,7-heptanedioic
acid (aka hept-1,7-dioic acid). Provide the product for step 1, and write the mechanisms for
steps 1 and 2. Use whatever reagents you might deem appropriate for each step.
O

OEt

O

step 1: esterification step 2: Claisen condensation
(has to be done under (better performed under
acidic conditions) basic conditions) O
EtOH EtONa
HO OH EtO OEt OEt
H
O O O O O
H
both CO2H will be
protonated since EtO EtO – can be a B or Nu
HO OH they are of same reactivity
(protontation will take As a Nu - the same ester will form
place either sequentially As a B - enolate will form; C – is a better
O O or simultaneously) Nu than O – ; also Nu addition will be
H H
intramolecular
EtOH O
Et H Et both carbonyl centers
EtO OEt
H OEt
O O will be attacked by EtOH/Nu;
HO OH they are of same reactivity work-up O O OEt
(Nu-addition will take
place either sequentially O
O O or simultaneously)
H H
~H EtO OEt

Et O O
Et
O O
H 2O OH2 EtO OEt

O O O O
H H H H

4 (20pts) Name the following compounds:
OH Br
4
Z-4-bromo-3-en-but-2-ol
2 OH has a higher priority
1 3
than C=C; C=C has Z O
stereochemistry
OH
2
1 OH ethyl phenyl ether
4
5 3 (also: ethoxybenzene)
O (R)-4-hydroxy-pentanoic acid
(also (4R)-hydroxy-pentanoic acid O
peroxyacid reacts with alkenes to give epoxides
works); CO2H has a higher priority
3 than OH H
2

1
cyclohexanecarboxaldehyde
O
2(S)-ethylcylohexanone "carboxaldehyde" implies CHO
order of priority on C2: i.e,. 1 C; hence the overall carbon
C1, C3, Et, H count is 7

2
5 (60pts) Fill in the blanks, assume a work-up step in each case, unless stated otherwise:
ester hydrolysis excess
O of HO – is assumed
O based on the product
2eq O O
OH
ONa acetal formation
OH
SN 2 reaction ketone and diol
O H under acdic
NaOAc is a OH conditions
good Nu O O O
due to charge Br
delocalization OMe
O
NH
O
Br
tBuOK
LDA is a base only (1eq)
2 eliminations tBu
LDA (xs) O O
(E2 and E2-like, followed
by deprotonation)
tBu OMe
N
alkynyl intermidiate
should be assumed H
based on O O E1cb
i) LDA is a base, and Nu-addition to leading to
there are 2 good LGs imine giving amine OMe H enone
tBu O
ii) alkyne moiety is in tBu
Br tBuOK (1eq)
the amine this compound is
not isolated
(i.e., no work-up) O
O
OMe
H /H2O PBr 3 H
(i.e., work-up)
tBu O OH

OH

LiA O
lH O
4
tBu reduction of carbonyl H
only LAH can be used NaOH
due to the acid CO2H
BH3 is a Lewis acid functionality
should react with BH 3 KMnO 4 KMnO 4
C=C (same as with (1eq) tBu
alkenes; the other Δ, H Δ, H
C=C remains intact)
BH 2 OH O
NaOH
aldol condensation
H between 2 aldehydes
H 2O2
tautomerization only one can act as Nu
tBu tBu either under bc it could be converted
tBu
acidic or basic to enolate
this two step sequence is identical to hydroboration conditions
of alkenes; for alkynes one C=C reacts, the other C=C keto-enol tautomerization
remains intact aldehyde will be more stable

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