12/27/2016

1,3Dioxanes,1,3Dioxolanes

OrganicChemistryPortal
Reactions>>ProtectingGroups>>Stability

1,3Dioxanes,1,3Dioxolanes

T.W.Green,P.G.M.Wuts,
ProtectiveGroupsinOrganicSynthesis,
WileyInterscience,NewYork,1999,308322,724727.

Stability
H2 O:

pH<1,100C

pH=1,RT

pH=4,RT

pH=9,RT

pH=12,RT

pH>12,100C

Bases:

LDA

NEt3 ,Py

tBuOK

Others:

DCC

SOCl2

Nucleophiles:

RLi

RMgX

RCuLi

Enolates

NH3 ,RNH2

NaOCH3

Electrophiles:

RCOCl

RCHO

CH3 I

Others:

:CCl2

Bu3 SnH

Reduction:

H2 /Ni

H2 /Rh

Zn/HCl

Na/NH3

LiAlH4

NaBH4

Oxidation:

KMnO4

OsO4

CrO3 /Py

RCOOOH

I2 ,Br2 ,Cl2

MnO2 /CH2 Cl2

General
1,3Dioxanesand1,3dioxolanescaneasilybepreparedfromcarbonylcompoundswith1,3propanediolor1,2ethanediolinthepresenceofaBrnstedoraLewisacidcatalyst.
1,3Diolsgivemorestablecompounds.Astandardprocedureforprotectionemploystoluenesulfonicacidascatalystinrefluxingtoluene,whichallowsthecontinuousremovalof
waterfromthereactionmixtureusingaDeanStarkapparatus.Amixtureoforthoestersormolecularsievescanalsoprovideeffectivewaterremovalthroughchemicalreactionor
physicalsequestration.

Cyclicacetalsofferstabilityagainstalltypesofnucleophilesandbases.
Deprotectionisoftenperformedbyacidcatalyzedtransacetalizationinacetoneorhydrolysisinwetsolventsorinaqueousacid.Somestrongoxidationagentsmaycleaveacetals
suchasHClO4inCH2Cl2.Cyclicketalsandacetalsasarulearestabletomildhighvalentchromiumreagents(PCC,PDC,Jones,etc.),butstronglyacidicreagentswilloxidize
themtothelactone,orrelatedcleavageproducts.AdditionofstrongLewisacidsenhancesthesensitivitytowardsoxidantssuchasKMnO4,andMCPBA.
ProtectionofCarbonylCompounds

Acyclicandcyclicacetalsofvariouscarbonylcompoundswereobtainedinexcellentyieldsinthepresenceoftrialkylorthoformateandacatalyticamountoftetrabutylammonium
tribromideinabsolutealcohol.Thisconvenient,mild,chemoselectivemethodallowsacetalizationofanaldehydeinthepresenceofketone,unsymmetricalacetalformation,and
toleratesacidsensitiveprotectinggroups.
R.Gopinath,Sk.J.Haque,B.K.Patel,J.Org.Chem.,2002,67,58425845.

Zirconiumtetrachloride(ZrCl4)isahighlyefficientandchemoselectivecatalystfortheacetalization,andinsitutransacetalizationofcarbonylcompoundsundermildreaction
conditions.
H.Firouzabadi,N.Iranpoor,B.Karimi,Synlett,1999,321323.

Varioustypesofcarbonylcompoundsareefficientlyconvertedtotheir1,3dioxanesbytheuseof1,3bis(trimethylsiloxy)propane(BTSP)andacatalyticamountofiodineunder
essentiallyneutralaproticcondition.
B.Karimi,B.Golshani,Synthesis,2002,784788.

Varioustypesofhydroxyacetophenonesareefficientlyconvertedintothecorrespondingcyclicacetalsinthepresenceofadiol,triisopropylorthoformate,andacatalyticamountof
cerium(III)trifluoromethanesulfonateundermildreactionconditions.
F.Ono,H.Takenaka,T.Fujikawa,M.Mori,T.Sato,Synthesis,2009,13181322.

http://www.organicchemistry.org/protectivegroups/carbonyl/dioxanesdioxolanes.htm

1/3

12/27/2016

1,3Dioxanes,1,3Dioxolanes

Aliphaticandaromaticketonescanbedirectlyconvertedintotheircorrespondingchloroketoneacetalsinverygoodyieldsusingiodobenzenedichlorideinethyleneglycolinthe
presenceof4molecularsievesatroomtemperature.
J.Yu,C.Zhang,Synthesis,2009,23242328.
OtherSynthesesofCyclicAcetals

Ammoniumsaltsthatcanactashydrogenbonddonorsexertaremarkableaccelerationontheratesoftheregioselectivearylationofelectronricholefinsbyarylhalidesinionic
liquidsandcommonsolvents.
J.Mo,J.Xiao,Angew.Chem.Int.Ed.,2006,45,41524157.

Anewpalladium(0)catalyzedthreecomponentreactionofsalicylicaldehydetriflates,ethyleneglycolvinylether,andvarioussecondarynucleophilicaminesinvolvinganinitial
internalHeckarylation,iminiumionformation,andsubsequenttandemcyclizationgivestertiary3aminoindanacetals.
A.Arefalk,M.Larhed,A.Hallberg,J.Org.Chem.,2005,70,938942.
Deprotection

Acetalsandketalsarereadilydeprotectedunderneutralconditionsinthepresenceofacetoneandindium(III)trifluoromethanesulfonateascatalystatroomtemperatureormild
microwaveheatingconditionstogivethecorrespondingaldehydesandketonesingoodtoexcellentyields.
B.T.Gregg,K.C.Golden,J.F.Quinn,J.Org.Chem.,2007,72,58905893.

Er(OTf)3isaverygentleLewisacidcatalystinthechemoselectivecleavageofalkylandcyclicacetalsandketalsatroomtemperatureinwetnitromethane.
R.Dalpozzo,A.DeNino,L.Maiuolo,M.Nardi,A.Procopio,A.Tagarelli,Synthesis,2004,496498.

Achemoselectivemethodforthecleavageofacetalsandketalsatroomtemperatureinwetnitromethanebyusingcatalyticcerium(III)triflateatalmostneutralpHispresented.
Highyieldsandselectivitymakethisprocedureparticularlyattractiveformultistepsynthesis.
R.Dalpozzo,A.DeNino,L.Maiuolo,A.Procopio,A.Tagarelli,G.Sindona,G.Bartoli,J.Org.Chem.,2002,67,90939095.

AconvenientdeprotectionofacyclicandcyclicO,OacetalsandO,Oketalsisachievedinexcellentyieldswithinminutesunderneutralconditionsinthepresenceofacatalytic
amountofiodine.Doublebonds,hydroxylgroups,acetategroups,andhighlyacidsensitivegroupssuchasfuryl,tertbutylethers,andketoximesaretolerated.
J.Sun,Y.Dong,L.Cao,X.Wang,S.Wang,Y.Hu,J.Org.Chem.,2004,69,89328934.

Deprotectionofacetalsandketalscanbeachievedbyusingacatalyticamountofsodiumtetrakis(3,5trifluoromethylphenyl)borate(NaBArF4)inwaterat30C.Forexample,a
quantitativeconversionof2phenyl1,3dioxolaneintobenzaldehydewasaccomplishedwithinfiveminutes.
C.C.Chang,B.S.Liao,S.T.Liu,Synlett,2007,283287.
ConversionofCyclicAcetalsandKetalstoOtherFunctionalGroups

Aldehydesandketoneswereprotectedastheirthioacetalsinthepresenceofacatalyticamountofiodine.Thesemildreactionconditionswerealsoappliedinthe
transthioacetalizationofO,Oacetals,O,Oketals,O,Sacetals,andacylals.
H.Firouzabadi,N.Iranpoor,H.Hazarkhani,J.Org.Chem.,2001,66,75277529.

http://www.organicchemistry.org/protectivegroups/carbonyl/dioxanesdioxolanes.htm

2/3

12/27/2016

1,3Dioxanes,1,3Dioxolanes

Anefficientoxidationofvariousacetals,includingopenchainacetals,1,3dioxanesand1,3dioxalanes,withmolecularoxygeninthepresenceofcatalyticamountsofNhydroxy
phthalimide(NHPI)andCo(OAc)2ascocatalystgaveesters.
B.Karimi,J.Rajabi,Synthesis,2003,23732377.

AnefficientoxidationofcyclicacetalsprovidedhydroxyalkylestersingoodyieldsinthepresenceofMCPBA.
J.Y.Kim,H.Rhee,M.Kim,J.KoreanChem.Soc.,2002,46,479483.

http://www.organicchemistry.org/protectivegroups/carbonyl/dioxanesdioxolanes.htm

3/3