Chemistry

234
Chapter 23 Problem Set
Carbonyl Condensation Chemistry
1) Draw the product formed from each of the aldol reactions/condensations below.
OH
H H 2O
2
O

OH
O O H 2O
+
H H

O 1. LDA, THF
-78 °C
2. Ph O
3. HO -, H 2O

O OH
H 2O
H
O

OH
O O H 2O

O 1. LDA, THF
-78 °C
2. O

3. H 2O

2) What starting material(s) is/are needed to prepare each compound below via an aldol reaction?
O

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 Chem. 234 – Chapter 23 Problem Set
3) Predict the major organic product formed from each of the Claisen Condensation Reactions.

1. NaOEt
O HOEt
2
Ph OEt 2. H + workup

1. NaOCH 3
OCH3 O HOCH 3
+
Ph OCH3 2. H + workup
O

O 1. NaOEt
O HOEt
+
EtO OEt 2. H + workup

1. NaOEt
O O HOEt
+
2. H + workup
Ph OEt

4) Each compound below undergoes a Dieckmann Condensation (Intramolecular Claisen). Predict the
major products for each.

O 1. NaOEt
OEt HOEt 2
EtO 2. H + workup products
O

1. NaOEt
O O HOEt
OEt 2. H + workup

O 1. NaOEt
HOEt
OEt 2. H + workup
O

5) Draw the complete electron pushing mechanism for the second reaction in question 4.

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 Chem. 234 – Chapter 23 Problem Set
6) What starting materials are needed to synthesize each compound below by a Crossed Claisen
Reaction?
O
O

O OEt

O O

H



Conjugate Addition
7) Predict the product for each Michael reaction below.

O
O O OH
+
Ph H 2O
OEt

O O O
OH
+
H 2O

O
O O OH
+
Ph OEt H 2O


8) Draw the product from the Robinson Annulation of each.

O
OH
+
O H 2O
O

O
O OH
+
H 2O

O O
OH
+
H 2O



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 Chem. 234 – Chapter 23 Problem Set
9) Identify what reagents you would use to prepare the compound below using a Robinson
Annulation reaction?

O

O



Part 5: Application to Synthesis
10)Fill in the missing reagents in the synthetic sequence below.
O O O
O
O O O
O

OEt OEt OEt

O O O O

Br

HO CN
CH2 O

11)Provide a reasonable mechanism for the reaction below. What is the driving force for this reaction?
O O
OH
H 2O
OH
O

12)Propose an efficient synthesis for the following transformation. Hint: You will need to use the
ozonolysis reaction from organic I.
O
?

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 Chem. 234 – Chapter 23 Problem Set
13)Challenge: The compound below cannot be prepared by direct alkylation of cyclohexanone.
Explain why not and provide an alternative route to carry out the transformation. Hint: at some
stage, methyl cuprate might be useful.

O O

14)Draw an electron pushing mechanism for the following reaction.
H 3CO O
1. NaOCH 3
O
O O 2. H 2O
O O
OCH3

















15)Devise a synthesis for the compound below starting with cycloheaxnone.
O O

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 Chem. 234 – Chapter 23 Problem Set
16)Devise a synthesis of the ketone below using the ester starting material provided. Your synthesis
must involve the use of a Claisen condensation.
O O

OEt








17)Devise an efficient synthesis for the following transformation.
O
O O

EtO OEt













18)Reaction Combo: Draw the organic products formed when butanal is treated with each reagent.
a) HO-, H2C=O, H2O
b) 1. LDA, THF, -78 oC; 2. PhCHO; 3. H2O
c) diethyl malonate, NaOEt, HOEt
d) CH3-Li then H+
e) NaBH4, CH3OH
f) HOCH2CH2CH2OH, H+
g) H3C-NH2, trace acid
h) (CH3)2NH, trace acid
i) H2CrO4
j) Br2, AcOH
k) Ph3P=CH-CH3
l) 1. LDA, THF, -78 oC; 2. H3C-I
m) HO-, H2O (rxn between two molecules of aldehyde)

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