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Chemistry234Chapter23ProblemSet
CarbonylCondensationChemistry1) Drawtheproductformedfromeachofthealdolreactions/condensationsbelow.
2) Whatstartingmaterial(s)is/areneededtoprepareeachcompoundbelowviaanaldolreaction?
H
O2
OHH2O
H H
O O+
OHH2O
O 1. LDA, THF -78 °C2. Ph O
3. HO-, H2O
OH
O
O O
OHH2O
OHH2O
O 1. LDA, THF -78 °C2. O
3. H2O
O
O
O
Chem.234–Chapter23ProblemSet
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3) PredictthemajororganicproductformedfromeachoftheClaisenCondensationReactions.
4) EachcompoundbelowundergoesaDieckmannCondensation(IntramolecularClaisen).Predictthemajorproductsforeach.
5) Drawthecompleteelectronpushingmechanismforthesecondreactioninquestion4.
Ph OEt
O2
1. NaOEt HOEt2. H+ workup
OCH3
O+
Ph OCH3
O1. NaOCH3 HOCH3
2. H+ workup
O
+EtO OEt
O 1. NaOEt HOEt2. H+ workup
O+
Ph OEt
O 1. NaOEt HOEt2. H+ workup
EtO
OOEt
O
1. NaOEt HOEt2. H+ workup
2products
O
OEt
O
OEt
O
O
1. NaOEt HOEt2. H+ workup
1. NaOEt HOEt2. H+ workup
Chem.234–Chapter23ProblemSet
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6) WhatstartingmaterialsareneededtosynthesizeeachcompoundbelowbyaCrossedClaisenReaction?
ConjugateAddition7) PredicttheproductforeachMichaelreactionbelow.
8) DrawtheproductfromtheRobinsonAnnulationofeach.
OO
OEtO
O
H
O
Ph
O+
OEt
OO OHH2O
O OOOHH2O
+
O+
Ph
O
OEt
O OHH2O
OHH2O
OHH2O
O
O
O
+
OO
+
O O+ OH
H2O
Chem.234–Chapter23ProblemSet
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9) IdentifywhatreagentsyouwouldusetopreparethecompoundbelowusingaRobinsonAnnulationreaction?
Part5:ApplicationtoSynthesis10) Fillinthemissingreagentsinthesyntheticsequencebelow.
11) Provideareasonablemechanismforthereactionbelow.Whatisthedrivingforceforthisreaction?
12) Proposeanefficientsynthesisforthefollowingtransformation.Hint:YouwillneedtousetheozonolysisreactionfromorganicI.
O
O
O O
OEt
OO
OEt
O
O O
CNHOOCH2
OEt
OO O
O
Br
O
O
OH
OHH2O
O
O
O?
Chem.234–Chapter23ProblemSet
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13) Challenge:Thecompoundbelowcannotbepreparedbydirectalkylationofcyclohexanone.Explainwhynotandprovideanalternativeroutetocarryoutthetransformation.Hint:atsomestage,methylcupratemightbeuseful.
14) Drawanelectronpushingmechanismforthefollowingreaction.
15) Deviseasynthesisforthecompoundbelowstartingwithcycloheaxnone.
O O
OO
H3CO
O1. NaOCH3
2. H2OO
O
OCH3O
O O
O
Chem.234–Chapter23ProblemSet
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16) Deviseasynthesisoftheketonebelowusingtheesterstartingmaterialprovided.YoursynthesismustinvolvetheuseofaClaisencondensation.
17) Deviseanefficientsynthesisforthefollowingtransformation.
18) ReactionCombo:Drawtheorganicproductsformedwhenbutanalistreatedwitheachreagent.a) HO-,H2C=O,H2Ob) 1.LDA,THF,-78oC;2.PhCHO;3.H2Oc) diethylmalonate,NaOEt,HOEtd) CH3-LithenH+e) NaBH4,CH3OHf) HOCH2CH2CH2OH,H+g) H3C-NH2,traceacidh) (CH3)2NH,traceacidi) H2CrO4j) Br2,AcOHk) Ph3P=CH-CH3l) 1.LDA,THF,-78oC;2.H3C-Im) HO-,H2O(rxnbetweentwomoleculesofaldehyde)
OEt
O O
EtO OEt
OOO
