Pleas Ce hꢀ d eo mꢀ ni oc ta ꢀ la dS jcu i se t nꢀ mc ea rginsꢀ
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ARTICLEꢀ
JournalꢀNameꢀ
1
Notesꢀandꢀreferencesꢀ
Joschekꢀ andꢀ P.ꢀ Hofmann,ꢀ Angew.ꢀ Chem.ꢀ Int.ꢀ Ed.,ꢀ 2001,ꢀ 40,ꢀ
DOI: 10.1039/C6SC03838G
1
Representativeꢀ reviewsꢀ onꢀ carboxylationꢀ ofꢀ organicꢀ
compounds:ꢀ(a)ꢀT.ꢀSakakura,ꢀJ.-C.ꢀChoiꢀandꢀH.ꢀYasuda,ꢀChem.ꢀ
Rev.,ꢀ2007,ꢀ 107,ꢀ2365–2387;ꢀ(b)ꢀS.ꢀN.ꢀRiduanꢀandꢀY.ꢀZhang,ꢀ
Daltonꢀ Trans.,ꢀ 2010,ꢀ 39,ꢀ 3347–3357;ꢀ (c)ꢀ M.ꢀ Cokoja,ꢀ C.ꢀ
Bruckmeier,ꢀ B.ꢀ Rieger,ꢀ W.ꢀ A.ꢀ Herrmann,ꢀ andꢀ F.ꢀ E.ꢀ Kühn,ꢀ
Angew.ꢀChem.ꢀInt.ꢀEd.,ꢀ2011,ꢀ50,ꢀ8510–8537;ꢀ(d)ꢀK.ꢀHuang,ꢀ
C.-L.ꢀSunꢀandꢀZ.-J.ꢀShi,ꢀChem.ꢀSoc.ꢀRev.,ꢀ2011,ꢀ40,ꢀ2435–2452;ꢀ
781-784;ꢀ(b)ꢀC.ꢀWerlé,ꢀC.ꢀBailly,ꢀL.ꢀKarmazin-Brelot,ꢀX.-F.ꢀLeꢀ
Goff,ꢀM.ꢀPfefferꢀandꢀJ.-P.ꢀDjukic,ꢀAngew.ꢀChem.ꢀInt.ꢀEd.,ꢀ2014,ꢀ
53,ꢀ 9827–9831.ꢀ Forꢀ otherꢀ 14-eletronꢀ rhodiumꢀ complexes,ꢀ
see:ꢀ(c)ꢀP.ꢀZhao,ꢀC.ꢀKrugꢀandꢀJ.ꢀF.ꢀHartwig,ꢀJ.ꢀAm.ꢀChem.ꢀSoc.,ꢀ
2005,ꢀ127,ꢀ12066–12073;ꢀ(d)ꢀA.ꢀB.ꢀChaplin,ꢀOrganometallics,ꢀ
2014,ꢀ33,ꢀ624–626;ꢀ(e)ꢀM.ꢀT.ꢀWhited,ꢀA.ꢀJ.ꢀKosanovichꢀandꢀD.ꢀ
E.ꢀ Janzen,ꢀ Organometallics,ꢀ 2014,ꢀ 33,ꢀ 1416−1422;ꢀ (f)ꢀ M.ꢀ
Hasegawa,ꢀY.ꢀSegawa,ꢀM.ꢀYamashitaꢀandꢀK.ꢀNozaki,ꢀAngew.ꢀ
Chem.ꢀInt.ꢀEd.,ꢀ2012,ꢀ51,ꢀ6956–6960.ꢀ
(
e)ꢀZ.ꢀWenzhenꢀandꢀL.ꢀXiaobing,ꢀChin.ꢀJ.ꢀCatal.,ꢀ2012,ꢀ33,ꢀ745–
7
9
1
56;ꢀ (f)ꢀY.ꢀTsujiꢀandꢀT.ꢀFujihara,ꢀChem.ꢀCommun.,ꢀ2012,ꢀ48,ꢀ
956–9964;ꢀ(g)ꢀI.ꢀOmae,ꢀCoord.ꢀChem.ꢀRev.,ꢀ2012,ꢀ256,ꢀ1384– 14 Similarꢀ strategiesꢀ toꢀ stabilizeꢀ 14-electronꢀ complexesꢀ inꢀ
405;ꢀ(h)ꢀX.ꢀCaiꢀandꢀB.ꢀXie,ꢀSynthesis,ꢀ2013,ꢀ45,ꢀ3305–3324;ꢀ
mechanisticꢀstudies:ꢀ(a)ꢀT.ꢀHayashi,ꢀM.ꢀTakahashi,ꢀY.ꢀTakayaꢀ
andꢀ M.ꢀ Ogasawara,ꢀ J.ꢀ Am.ꢀ Chem.ꢀ Soc.,ꢀ 2002,ꢀ 124,ꢀ 5052–
5058;ꢀ(b)ꢀC.ꢀKrugꢀandꢀJ.ꢀF.ꢀHartwig,ꢀOrganometallics,ꢀ2004,ꢀ23,ꢀ
4594–4607.ꢀ
(
i)ꢀ J.ꢀ Takayaꢀ andꢀ N.ꢀ Iwasawa,ꢀ Scienceꢀ ofꢀ Synthesis,ꢀ C-1ꢀ
BuildingꢀBlocksꢀinꢀOrganicꢀSynthesis,ꢀ2014,ꢀ1,ꢀ281–307;ꢀ(j)ꢀQ.ꢀ
Liu,ꢀL.ꢀWu,ꢀR.ꢀJackstellꢀandꢀM.ꢀBeller,ꢀNat.ꢀCommun.,ꢀ2015,ꢀ6,ꢀ
5
933.ꢀꢀ
15 P.ꢀHofmann,ꢀC.ꢀMeier,ꢀW.ꢀHiller,ꢀM.ꢀHeckel,ꢀJ.ꢀRiedeꢀandꢀM.ꢀU.ꢀ
Schmidt,ꢀJ.ꢀOrganomet.ꢀChem.,ꢀ1995,ꢀ490,ꢀ51–70.ꢀ
3
16 ConsideredꢀfromꢀthisꢀstabilizationꢀeffectꢀofꢀPCy ,ꢀtheꢀroleꢀofꢀ
DMAꢀunderꢀtheꢀcatalyticꢀconditionsꢀmightꢀbeꢀsuppressionꢀofꢀ
2
3
T.ꢀ Suga,ꢀ H.ꢀ Mizuno,ꢀ J.ꢀ Takayaꢀ andꢀ N.ꢀ Iwasawa,ꢀ Chem.ꢀ
Commun.,ꢀ2014,ꢀ50,ꢀ14360–14363.ꢀ
Forꢀ catalyticꢀ C–Hꢀ bondꢀ carboxylationꢀ ofꢀ relativelyꢀ acidicꢀ
aromaticꢀ compounds,ꢀ see:ꢀ (a)ꢀ I.ꢀ I.ꢀ F.ꢀ Boogaertsꢀ andꢀ S.ꢀ P.ꢀ
Nolan,ꢀJ.ꢀAm.ꢀChem.ꢀSoc.,ꢀ2010,ꢀ132,ꢀ8858–8859;ꢀ(b)ꢀI.ꢀI.ꢀF.ꢀ
Boogaerts,ꢀG.ꢀC.ꢀFortman,ꢀM.ꢀR.ꢀL.ꢀFurst,ꢀC.ꢀS.ꢀJ.ꢀCazinꢀandꢀS.ꢀP.ꢀ
theꢀ catalystꢀ decomposition.ꢀ Presumably,ꢀ itꢀ weaklyꢀ
coordinatesꢀ toꢀ theꢀ vacantꢀ siteꢀ ofꢀ unstableꢀ 14-electronꢀ
complexes.ꢀ
Nolan,ꢀ Angew.ꢀ Chem.ꢀ Int.ꢀ Ed.,ꢀ 2010,ꢀ 49,ꢀ 8674–8677;ꢀ (c)ꢀ L.ꢀ 17 J.-C.ꢀ Choi,ꢀ andꢀ T.ꢀ Sakakura,ꢀ J.ꢀ Am.ꢀ Chem.ꢀ Soc.,ꢀ 2003,ꢀ 125,ꢀ
Zhang,ꢀJ.ꢀCheng,ꢀT.ꢀOhishiꢀandꢀZ.ꢀHou,ꢀAngew.ꢀChem.ꢀInt.ꢀEd.,ꢀ
7762–7763.ꢀ
010,ꢀ49,ꢀ8670–8673;ꢀ(d)ꢀI.ꢀI.ꢀF.ꢀBoogaertsꢀandꢀS.ꢀP.ꢀNolan,ꢀ 18 TheꢀGCꢀanalysisꢀofꢀtheꢀliquidꢀphaseꢀrevealedꢀtheꢀformationꢀofꢀ
2
Chem.ꢀ Commun.,ꢀ 2011,ꢀ 47,ꢀ 3021–3024;ꢀ (e)ꢀ H.ꢀ Inomata,ꢀ K.ꢀ
Ogata,ꢀS.ꢀFukuzawaꢀandꢀZ.ꢀHou,ꢀOrg.ꢀLett.,ꢀ2012,ꢀ14,ꢀ3986–
aꢀ veryꢀ smallꢀ amountꢀ ofꢀ tolueneꢀ (0.002ꢀ mmol,ꢀ TONꢀ =ꢀ 0.2),ꢀ
whichꢀ mightꢀ beꢀ generatedꢀ byꢀ undesiredꢀ reductiveꢀ
eliminationꢀfromꢀRh(H)(Me)(Ph)(dcype)ꢀB.ꢀ
3
989.ꢀ
4
5
AlMe1.5(OEt)1.5ꢀ wasꢀ preparedꢀ fromꢀ AlMe
3
ꢀ andꢀ 2ꢀ equiv.ꢀ ofꢀ 19 InsufficientꢀintroductionꢀofꢀCO ꢀledꢀtoꢀirreproducibleꢀresults.ꢀ
2
EtOH.ꢀ Theꢀ 1ꢀ :ꢀ 1ꢀ sharpꢀ peaksꢀ ofꢀ methylꢀ groupꢀ andꢀ ethoxyꢀ
groupꢀindicateꢀthisꢀcompositionꢀandꢀitsꢀdiscreteꢀstructure.ꢀAꢀ 20 Accordingꢀtoꢀ PꢀNMRꢀanalysis,ꢀtheꢀreactionꢀmixtureꢀincludedꢀ
SeeꢀSIꢀforꢀtheꢀpracticalꢀexperimentalꢀprocedure.ꢀ
31
tetramerꢀ structureꢀ hasꢀ beenꢀ postulatedꢀ forꢀ theꢀ relatedꢀ
compound.ꢀSee:ꢀJ.ꢀTurunen,ꢀT.ꢀT.ꢀPakkanenꢀandꢀB.ꢀLöfgren,ꢀJ.ꢀ
Mol.ꢀCatal.,ꢀ1997,ꢀ123,ꢀ35–42ꢀandꢀrefꢀ2.ꢀ
aꢀsmallꢀamountꢀofꢀRh(OAc)(dcype)ꢀEꢀatꢀlowerꢀconcentrationꢀ
3
ofꢀPCy ꢀandꢀitꢀaffectedꢀconcentrationꢀofꢀfreeꢀPCy .ꢀButꢀitꢀwasꢀ
3
trivialꢀ soꢀ thatꢀ linearꢀ correlationꢀ wasꢀ mostlyꢀ maintainedꢀ
throughoutꢀtheꢀexperiment.ꢀ
Examplesꢀ ofꢀ stoichiometricꢀ C–Hꢀ bondꢀ activationꢀ byꢀ
alkylrhodium(I)ꢀcomplexes:ꢀ(a)ꢀR.ꢀT.ꢀPrice,ꢀR.ꢀA.ꢀAndersenꢀandꢀ 21 Itꢀ shouldꢀ beꢀ notedꢀ thatꢀ weꢀ usedꢀ Chemistation™ꢀ (Tokyoꢀ
E.ꢀL.ꢀMuetterties,ꢀJ.ꢀOrganomet.ꢀChem.,ꢀ1989,ꢀ376,ꢀ407–417;ꢀ
Theꢀ intermediacyꢀ ofꢀ 14-electronꢀ alkylrhodium(I)ꢀ wasꢀ
postulated,ꢀhowever,ꢀsufficientꢀexperimentalꢀsupportsꢀwereꢀ
notꢀprovided.ꢀSee:ꢀ(b)ꢀS.ꢀE.ꢀBoyd,ꢀL.ꢀD.ꢀField,ꢀT.ꢀW.ꢀHambleyꢀ
andꢀM.ꢀG.ꢀPartridge,ꢀOrganometallics,ꢀ1993,ꢀ12,ꢀ1720–1724.ꢀꢀ
Stoichiometricꢀcarboxylationꢀofꢀarylrhodium(I)ꢀcomplexes:ꢀ(a)ꢀ
I.ꢀ S.ꢀ Kolomnikov,ꢀ A.ꢀ O.ꢀ Gusev,ꢀ T.ꢀ S.ꢀ Belopotapova,ꢀ M.ꢀ K.ꢀ
Grigoryan,ꢀT.ꢀV.ꢀLysyak,ꢀY.ꢀT.ꢀStruchkovꢀandꢀM.ꢀE.ꢀVol’pin,ꢀJ.ꢀ
Organomet.ꢀChem.,ꢀ1974,ꢀ69,ꢀC10–C12;ꢀ(b)ꢀD.ꢀJ.ꢀDarensbourg,ꢀ
Rikakikaiꢀ Co.ꢀ Ltd.)ꢀ forꢀ heatingꢀ aꢀ reactionꢀ mixtureꢀ inꢀ otherꢀ
experimentsꢀ includingꢀ Schemeꢀ 9.ꢀ Thisꢀ apparatusꢀ coolsꢀ theꢀ
systemꢀ justꢀ aboveꢀ theꢀ liquidꢀ phaseꢀ toꢀ maintainꢀ gentleꢀ
refluxing.ꢀOnꢀtheꢀotherꢀhand,ꢀexperimentsꢀinꢀTableꢀ1–3ꢀwereꢀ
carriedꢀ outꢀ inꢀ anꢀ oilꢀ bath,ꢀ whichꢀ doesꢀ notꢀ haveꢀ aꢀ coolingꢀ
systemꢀ forꢀ aꢀ practicalꢀ reason.ꢀ Suchꢀ smallꢀ differenceꢀ alsoꢀ
affectedꢀtheꢀresults.ꢀForꢀexample,ꢀTONsꢀofꢀBzOHꢀandꢀAcOHꢀ
wereꢀ 15ꢀ andꢀ 54ꢀ respectively,ꢀ whenꢀ theꢀ reactionꢀ inꢀ entryꢀ 1ꢀ
(Tableꢀ1)ꢀwasꢀcarriedꢀoutꢀusingꢀChemistation™.ꢀ
6
G.ꢀGrötsch,ꢀP.ꢀWiegreffe,ꢀandꢀA.ꢀL.ꢀRheingold,ꢀInorg.ꢀChem.,ꢀ 22 DecreaseꢀofꢀCO ꢀshouldꢀaffectꢀtheꢀresultsꢀinꢀlongerꢀreactionꢀ
2
1
987,ꢀ26,ꢀ3827–3830.ꢀ
time.ꢀ Theꢀ amountꢀ ofꢀ aceticꢀ acidꢀ inꢀ Schemeꢀ 9ꢀ (TONꢀ =ꢀ 60)ꢀ
suggestsꢀaceticꢀacidꢀdoesꢀnotꢀformꢀsoꢀmuchꢀatꢀtheꢀlaterꢀstageꢀ
ofꢀtheꢀreaction.ꢀ
7
8
L.ꢀYangꢀandꢀH.ꢀHuang,ꢀChem.ꢀRev.,ꢀ2015,ꢀ115,ꢀ3468–3517.ꢀ
H.ꢀ Mizuno,ꢀ J.ꢀ Takayaꢀ andꢀ N.ꢀ Iwasawa,ꢀ J.ꢀ Am.ꢀ Chem.ꢀ Soc.,ꢀ
2011,ꢀ133,ꢀ1251–1253.ꢀ
(a)ꢀK.ꢀGaoꢀandꢀN.ꢀYoshikai,ꢀChem.ꢀCommun.,ꢀ2012,ꢀ48,ꢀ4305–
23 Theꢀ experimentsꢀ atꢀ higherꢀ temperatureꢀ wereꢀ unsuccessfulꢀ
owingꢀtoꢀtheꢀsensitivityꢀofꢀourꢀequipment.ꢀ
9
4
2
307;ꢀ(b)ꢀK.ꢀGao,ꢀR.ꢀPairaꢀandꢀN.ꢀYoshikai,ꢀAdv.ꢀSynth.ꢀCatal.,ꢀ 24 Additionꢀ ofꢀ anꢀ appropriateꢀ ligandꢀ enablesꢀ observationꢀ ofꢀ
014,ꢀ356,ꢀ1486–1490.ꢀ
methylrhodium(I)ꢀ complexꢀ inꢀ suchꢀ Rh-Cl/Al-Meꢀ
transmetallationꢀ equilibrium.ꢀ Forꢀ example,ꢀ theꢀ reactionꢀ ofꢀ
RhCl(PCy )(dcype)ꢀFꢀwithꢀAlMe ꢀgaveꢀRhMe(PCy )(dcype)ꢀ2ꢀasꢀ
1
1
0 B.ꢀZhou,ꢀY.ꢀHuꢀandꢀC.ꢀWang,ꢀAngew.ꢀChem.ꢀInt.ꢀEd.,ꢀ2015,ꢀ54,ꢀ
3659–13663.ꢀꢀ
1
3
3
3
1 Forꢀ additionꢀ toꢀ aldehydesꢀ usingꢀ silanesꢀ asꢀ aꢀ stoichiometricꢀ
reductant,ꢀsee:ꢀ(a)ꢀY.ꢀFukumoto,ꢀK.ꢀSawada,ꢀM.ꢀHagihara,ꢀN.ꢀ
ChataniꢀandꢀS.ꢀMurai,ꢀAngew.ꢀChem.ꢀInt.ꢀEd.,ꢀ2002,ꢀ41,ꢀ2779–
1.5 1.5
aꢀmajorꢀproduct.ꢀInterestingly,ꢀuseꢀofꢀAlMe (OEt) ꢀresultedꢀ
inꢀ noꢀ reactionꢀ underꢀ theꢀ similarꢀ conditions.ꢀ Theseꢀ resultsꢀ
mightꢀ haveꢀ relationꢀ withꢀ theꢀ betterꢀ resultsꢀ obtainedꢀ usingꢀ
2
theꢀlatterꢀreagentꢀinꢀtheꢀcarboxylationꢀreaction. ꢀ
2
781;ꢀ(b)ꢀY.ꢀKuninobu,ꢀY.ꢀNishina,ꢀT.ꢀTakeuchiꢀandꢀK.ꢀTakai,ꢀ
Angew.ꢀChem.ꢀInt.ꢀEd.,ꢀ2007,ꢀ46,ꢀ6518–6520;ꢀ(c)ꢀB.-J.ꢀLiꢀandꢀ
Z.-J.ꢀShi,ꢀChem.ꢀSci.,ꢀ2011,ꢀ2,ꢀ488–493.ꢀ
Cy2
P
Cy2
P
Cy2
P
5
equiv.
5 equiv.
AlMe3
Cl
PCy3
Cl
Me
1
2 (a)ꢀT.ꢀG.ꢀOstapowicz,ꢀM.ꢀHölscherꢀandꢀW.ꢀLeitner,ꢀChem.ꢀEur.ꢀ
J.,ꢀ2011,ꢀ17,ꢀ10329–10338;ꢀ(b)ꢀH.-L.ꢀQin,ꢀJ.-B.ꢀHan,ꢀJ.-H.ꢀHaoꢀ
andꢀE.ꢀA.ꢀB.ꢀKantchev,ꢀGreenꢀChem.,ꢀ2014,ꢀ16,ꢀ3224–3229;ꢀ(c)ꢀ
S.ꢀV.ꢀC.ꢀVummaleti,ꢀG.ꢀTalarico,ꢀS.ꢀP.ꢀNolan,ꢀL.ꢀCavalloꢀandꢀA.ꢀ
Poater,ꢀOrg.ꢀChem.ꢀFront.,ꢀ2016,ꢀ3,ꢀ19–23.ꢀ
Rh
Rh
Rh
2
benzene
rt, 11 h
P
Cy2
PCy3
rt, 1.5 h
P
Cy2
PCy3
P
Cy2
1
F
2
2
5 Thereꢀ wouldꢀ alsoꢀ beꢀ anꢀ equilibriumꢀ betweenꢀ 1ꢀ andꢀ
RhPh(dcype)ꢀCꢀinꢀaꢀsimilarꢀmanner.ꢀ
8
ꢀ|ꢀJ.ꢀName.,ꢀ2012,ꢀ00,ꢀ1-3ꢀ
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