Page 7 of 9
Journal of the American Chemical Society
asꢀanꢀinternalꢀstandard,ꢀtheꢀreactionꢀmixtureꢀwasꢀanalyzedꢀ
byꢀGC.ꢀTheꢀproductsꢀwereꢀisolatedꢀbyꢀflashꢀcolumnꢀchro-
matographyꢀonꢀsilicaꢀgelꢀ(PE:EAꢀ=ꢀ50:1).ꢀ
Generalꢀ procedureꢀ forꢀ two-foldꢀ functionalizationꢀ
ofꢀ alkanes.ꢀ Inꢀ anꢀ argon-filledꢀ glovebox,ꢀ aꢀ thick-wallꢀ
Kontesꢀflaskꢀ(10ꢀmL)ꢀwasꢀchargedꢀwithꢀ(PSCOP)IrHClꢀ(1)ꢀ
(1.0ꢀmol%),ꢀNaOtBuꢀ(1.2ꢀmol%),ꢀalkaneꢀ(2.0ꢀmL)ꢀandꢀTBEꢀ
(0.50ꢀmmol).ꢀTheꢀflaskꢀwasꢀsealedꢀandꢀstirredꢀinꢀaꢀheatedꢀ
andꢀ Technologyꢀ Commissionꢀ ofꢀ Shanghaiꢀ Municipalityꢀ
(17JC1401200)ꢀsupportꢀthisꢀwork.ꢀ
1
2
3
4
5
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7
8
9
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REFERENCES
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ture,ꢀ ( PDI)FeBr
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ꢀ (10.0ꢀ mol%),ꢀ NaBHEt
3
ꢀ (20.0ꢀ mol%),ꢀ
(
(
TMSO)
2
MeSiHꢀ (0.5ꢀ mmol)ꢀ wereꢀ addedꢀ toꢀ theꢀ solutionꢀ
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
(
andꢀtheꢀsolutionꢀwasꢀstirredꢀatꢀroomꢀtemperatureꢀforꢀ12ꢀh.ꢀ
Theꢀreactionꢀmixtureꢀthenꢀpassedꢀthroughꢀaꢀsilicaꢀgelꢀplugꢀ
withꢀ n-pentaneꢀ asꢀ theꢀ eluentꢀ toꢀ giveꢀ theꢀ pureꢀ product.ꢀ
Theꢀsilylationꢀproductꢀthenꢀunderwentꢀtheꢀcarbonylationꢀ
followingꢀ theꢀ generalꢀ procedureꢀ describedꢀ above.ꢀ Theꢀ
crudeꢀfinalꢀproductꢀwasꢀanalyzedꢀbyꢀGCꢀwithꢀ50ꢀµLꢀmesit-
yleneꢀasꢀanꢀinternalꢀstandard.ꢀTheꢀproductꢀwasꢀthenꢀfur-
therꢀ isolatedꢀ throughꢀ aꢀ silicaꢀ gelꢀ plugꢀ (n-hexane:EAꢀ =ꢀ
Che,ꢀC.-M.ꢀAngew.ꢀChem.ꢀInt.ꢀEd.ꢀ2014,ꢀ53,ꢀ798.ꢀ(c)ꢀHartwig,ꢀJ.ꢀF.;ꢀ
Larsen,ꢀM.ꢀA.ꢀACSꢀCent.ꢀSci.ꢀ2016,ꢀ2,ꢀ281.ꢀ
(4)ꢀ
ꢀ(a)ꢀDíaz-Requejo,ꢀM.ꢀM.;ꢀPérez,ꢀP.ꢀJ.ꢀChem.ꢀRev.ꢀ2008,ꢀ
108,ꢀ3379.ꢀ(b)ꢀThu,ꢀH.-Y.;ꢀTong,ꢀS.-M.;ꢀHuang,ꢀJ.-S.;ꢀChan,ꢀL.-F.;ꢀ
Deng,ꢀQ.-H.;ꢀChe,ꢀC.-M.ꢀAngew.ꢀ Chem.ꢀ Int.ꢀ Ed.ꢀ 2008,ꢀ47,ꢀ9747.ꢀ
(c)ꢀ Caballero,ꢀ A.;ꢀ Despagnet-Ayoub,ꢀ E.;ꢀ Marꢀ Díaz-Requejo,ꢀ M.;ꢀ
Díaz-Rodríguez,ꢀA.;ꢀGonzález-Núñez,ꢀM.ꢀE.;ꢀMello,ꢀR.;ꢀMuñoz,ꢀB.ꢀ
K.;ꢀOjo,ꢀW.-S.;ꢀAsensio,ꢀG.;ꢀEtienne,ꢀM.;ꢀPérez,ꢀP.ꢀJ.ꢀScienceꢀ2011,ꢀ
3
32,ꢀ835.ꢀ(d)ꢀLiao,ꢀK.;ꢀNegretti,ꢀS.;ꢀMusaev,ꢀD.ꢀG.;ꢀBacsa,ꢀJ.;ꢀDavies,ꢀ
5
0:1).ꢀ
Generalꢀ procedureꢀ forꢀ aminomethylationꢀ ofꢀ al-
H.ꢀM.ꢀL.ꢀNatureꢀ2016,ꢀ533,ꢀ230.ꢀꢀꢀ
(5)ꢀ
(a)ꢀ Meunier,ꢀ B.;ꢀ deꢀ Visser,ꢀ S.ꢀ P.;ꢀ Shaik,ꢀ S.ꢀ Chem.ꢀ Rev.ꢀ
kanes.ꢀ Inꢀ anꢀ argon-filledꢀ glovebox,ꢀ aꢀ thick-wallꢀ Kontesꢀ
flaskꢀ (5ꢀ mL)ꢀ wasꢀ chargedꢀ withꢀ (PSCOP)IrHClꢀ (1)ꢀ (1.0ꢀ
mol%),ꢀ NaOtBuꢀ (1.2ꢀ mol%),ꢀ alkaneꢀ (2.0ꢀ mL)ꢀ andꢀ TBEꢀ
2
004,ꢀ104,ꢀ3947.ꢀ(b)ꢀOrtizꢀdeꢀMontellano,ꢀP.ꢀR.ꢀChem.ꢀRev.ꢀ2010,ꢀ
1
10,ꢀ932.ꢀ
6)ꢀ
(
(a)ꢀ Wenzel,ꢀ T.ꢀ T.;ꢀ Bergman,ꢀ R.ꢀ G.ꢀ J.ꢀ Am.ꢀ Chem.ꢀ Soc.ꢀ
(
0.50ꢀmmol).ꢀTheꢀflaskꢀwasꢀsealedꢀwithꢀaꢀTeflonꢀplugꢀun-
1986,ꢀ 108,ꢀ 4856.ꢀ (b)ꢀ Jones,ꢀ W.ꢀ D.;ꢀ Feher,ꢀ F.ꢀ J.ꢀ Organometallicsꢀ
1983,ꢀ2,ꢀ562.ꢀ
derꢀanꢀargonꢀatmosphere,ꢀandꢀtheꢀsolutionꢀwasꢀstirredꢀinꢀaꢀ
o
o
(
7)ꢀ
(a)ꢀChen,ꢀH.;ꢀSchlecht,ꢀS.;ꢀSemple,ꢀT.ꢀC.;ꢀHartwig,ꢀJ.ꢀF.ꢀ
2
00ꢀ Cꢀorꢀ190ꢀ Cꢀoilꢀbathꢀforꢀallottedꢀmin.ꢀAfterꢀthat,ꢀtheꢀ
flaskꢀwasꢀcooledꢀtoꢀroomꢀtemperature.ꢀAꢀ5-mLꢀvialꢀwithꢀaꢀ
magneticꢀstirringꢀbarꢀwasꢀchargedꢀwithꢀRh(acac)(CO) ꢀ(20ꢀ
Scienceꢀ 2000,ꢀ 287,ꢀ 1995.ꢀ (b)ꢀ Mkhalid,ꢀ I.ꢀ A.ꢀ I.;ꢀ Barnard,ꢀ J.ꢀ H.;ꢀ
Marder,ꢀT.ꢀB.;ꢀMurphy,ꢀJ.ꢀM.;ꢀHartwig,ꢀJ.ꢀF.ꢀChem.ꢀRev.ꢀ2010,ꢀ110,ꢀ
2
8
90.ꢀꢀ
8)ꢀ
S.ꢀJ.ꢀAm.ꢀChem.ꢀSoc.ꢀ1999,ꢀ121,ꢀ4086.ꢀ
9)ꢀ Kumar,ꢀA.;ꢀZhou,ꢀT.;ꢀEmge,ꢀT.ꢀJ.;ꢀMironov,ꢀO.;ꢀSaxton,ꢀ
mMꢀsolutionꢀinꢀtoluene)ꢀandꢀL1ꢀinꢀtheꢀgloveꢀbox.ꢀTheꢀmix-
tureꢀ wasꢀ stirredꢀ forꢀ 5ꢀ min,ꢀ followedꢀ byꢀ theꢀ additionꢀ ofꢀ
amineꢀ(1ꢀequivꢀrelativeꢀtoꢀTBE).ꢀTheꢀsolutionꢀderivedꢀfromꢀ
alkaneꢀdehydrogenationꢀwasꢀthenꢀaddedꢀtoꢀtheꢀ5-mLꢀvial.ꢀ
Theꢀvialꢀwasꢀtransferꢀtoꢀaꢀ50ꢀmLꢀautoclave.ꢀTheꢀautoclaveꢀ
(
Liu,ꢀF.;ꢀPak,ꢀE.ꢀB.;ꢀSingh,ꢀB.;ꢀJensen,ꢀC.ꢀM.;ꢀGoldman,ꢀA.ꢀ
(
R.ꢀJ.;ꢀKrogh-Jespersen,ꢀK.;ꢀGoldman,ꢀA.ꢀS.ꢀJ.ꢀAm.ꢀChem.ꢀSoc.ꢀ2015,ꢀ
137,ꢀ9894.ꢀ
wasꢀ purgedꢀ withꢀ H
2
ꢀ threeꢀ timesꢀ andꢀ thenꢀ chargedꢀ withꢀ
(10)ꢀ Mindiolaꢀ andꢀ Baikꢀ reportedꢀ aꢀ terminallyꢀ selectiveꢀ al-
kaneꢀ dehydrogenationꢀ catalyzedꢀ byꢀ aꢀ pincerꢀ titaniumꢀ complex,ꢀ
albeitꢀ withꢀ lowꢀ TONs.ꢀ See:ꢀ (a)ꢀ Solowey,ꢀ D.ꢀ P.;ꢀ Mane,ꢀ M.ꢀ V.;ꢀ
Kurogi,ꢀT.;ꢀCarroll,ꢀP.ꢀJ.;ꢀManor,ꢀB.ꢀC.;ꢀBaik,ꢀM.-H.;ꢀMindiola,ꢀD.ꢀJ.ꢀ
Nat.ꢀChem.ꢀ2017,ꢀ9,ꢀ1126.ꢀPhotocatalyticꢀalkaneꢀdehydrogenationꢀ
COꢀ(5ꢀbar)ꢀandꢀH ꢀ(25ꢀbar).ꢀTheꢀautoclaveꢀwasꢀheatedꢀforꢀ
2
allottedꢀ timeꢀ andꢀ cooledꢀ inꢀ anꢀ icyꢀ bath.ꢀ Theꢀ gasesꢀ wereꢀ
carefullyꢀreleasedꢀinꢀaꢀwell-ventilatedꢀhood.ꢀAfterꢀaddingꢀ
mesityleneꢀ (50ꢀ µL)ꢀ asꢀ anꢀ internalꢀ standard,ꢀ theꢀ reactionꢀ
mixtureꢀwasꢀanalyzedꢀbyꢀGC.ꢀ
3 2
usingꢀ RhCl(CO)(PMe ) ꢀ wasꢀ shownꢀ toꢀ giveꢀ improvedꢀ terminalꢀ
selectivity.ꢀ See:ꢀ (b)ꢀ Chowdhury,ꢀ A.ꢀ D.;ꢀ Weding,ꢀ N.;ꢀ Julis,ꢀ J.;ꢀ
Franke,ꢀR.;ꢀJackstell,ꢀR.;ꢀBeller,ꢀM.ꢀAngew.ꢀChem.ꢀInt.ꢀEd.ꢀ2014,ꢀ53,ꢀ
6477.ꢀ
■
ASSOCIATED CONTENT
(
11)ꢀ
675.ꢀ
(12)ꢀ vanꢀLeeuwen,ꢀP.ꢀW.ꢀN.ꢀM.,ꢀInꢀRhodiumꢀCatalyzedꢀHy-
Franke,ꢀR.;ꢀSelent,ꢀD.;ꢀBörner,ꢀA.ꢀChem.ꢀRev.ꢀ2012,ꢀ112,ꢀ
Supporting Information
5
TheꢀSupportingꢀInformationꢀisꢀavailableꢀfreeꢀofꢀchargeꢀonꢀtheꢀ
ACSꢀPublicationsꢀwebꢀsiteꢀatꢀDOI:ꢀ
droformylation;ꢀ vanꢀ Leeuwen,ꢀ P.ꢀ W.ꢀ N.ꢀ M.;ꢀ Claver,ꢀ C.,ꢀ Ed.;ꢀ
Springer:ꢀDordrecht,ꢀNetherlands,ꢀ2002,ꢀppꢀ1-13.ꢀ
(13)ꢀ Sakakura,ꢀ T.;ꢀ Tanaka,ꢀ M.ꢀ J.ꢀ Chem.ꢀ Soc.,ꢀ Chem.ꢀ
Commun.ꢀ1987,ꢀ758.ꢀ
(14)ꢀ (a)ꢀ Sakakura,ꢀ T.;ꢀ Sodeyama,ꢀ T.;ꢀ Sasaki,ꢀ K.;ꢀ Wada,ꢀ K.;ꢀ
Tanaka,ꢀM.ꢀ J.ꢀ Am.ꢀ Chem.ꢀ Soc.ꢀ 1990,ꢀ112,ꢀ7221.ꢀ(b)ꢀBoese,ꢀW.ꢀT.;ꢀ
Goldman,ꢀA.ꢀS.ꢀJ.ꢀAm.ꢀChem.ꢀSoc.ꢀ1992,ꢀ114,ꢀ350.ꢀ
■
AUTHOR INFORMATION
Corresponding Author
*huangzh@sioc.ac.cn.ꢀ
Notes
Theꢀauthorsꢀdeclareꢀnoꢀcompetingꢀfinancialꢀinterest.ꢀ
(
15)ꢀ Jaynes,ꢀ B.ꢀ S.;ꢀ Hill,ꢀ C.ꢀ L.ꢀ J.ꢀ Am.ꢀ Chem.ꢀ Soc.ꢀ 1995,ꢀ 117,ꢀ
704.ꢀ
(16)ꢀ (a)ꢀ Goldman,ꢀ A.ꢀ S.;ꢀ Roy,ꢀ A.ꢀ H.;ꢀ Huang,ꢀ Z.;ꢀ Ahuja,ꢀ R.;ꢀ
4
■
ACKNOWLEDGMENT
Schinski,ꢀ W.;ꢀ Brookhart,ꢀ M.ꢀ Scienceꢀ 2006,ꢀ 312,257.ꢀ (b)ꢀ
Dobereiner,ꢀ G.ꢀ E.;ꢀ Yuan,ꢀ J.;ꢀ Schrock,ꢀ R.ꢀ R.;ꢀ Goldman,ꢀ A.ꢀ S.;ꢀ
Hackenberg,ꢀJ.ꢀD.ꢀJ.ꢀ Am.ꢀ Chem.ꢀ Soc.ꢀ 2013,ꢀ135,ꢀ12572.ꢀ(c)ꢀJia,ꢀX.;ꢀ
Qin,ꢀ C.;ꢀ Friedberger,ꢀ T.;ꢀ Guan,ꢀ Z.;ꢀ Huang,ꢀ Z.ꢀ Sci.ꢀ Adv.ꢀ 2016,ꢀ 2,ꢀ
e1501591.ꢀ
Nationalꢀ Naturalꢀ Scienceꢀ Foundationꢀ ofꢀ Chinaꢀ ꢀ (21422209,ꢀ
1432011),ꢀ Ministryꢀ ofꢀ Scienceꢀ andꢀ Technologyꢀ ofꢀ Chinaꢀ
2016YFA0202900,ꢀ2015CB856600),ꢀChineseꢀAcademyꢀofꢀSci-
encesꢀ (XDB20000000,ꢀ QYZDB-SSW-SLH016),ꢀ andꢀ Scienceꢀ
2
(
(
17)ꢀ Ahuja,ꢀR.;ꢀPunji,ꢀB.;ꢀFindlater,ꢀM.;ꢀSupplee,ꢀC.;ꢀSchinski,ꢀ
W.;ꢀBrookhart,ꢀM.;ꢀGoldman,ꢀA.ꢀS.ꢀNat.ꢀChem.ꢀ2011,ꢀ3,ꢀ167.ꢀ
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