C 1 -Symmetric Binap Derivative Featuring Single Diferrocenylphosphino-Donor Moiety - Enomoto et al. - Unknown - Unknown

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C1-SymmetricBinapDerivativeFeaturingSingleDiferrocenylphosphino-DonorMoietyYuukiEnomoto,†HirokiIchiryu,†HaoHu,†,‡YasuyukiUra,§andMasamichiOgasawara*,††DepartmentofNaturalScience,GraduateSchoolofScienceandTechnology,TokushimaInternationalScienceInstitute,andResearchClusteron"InnovativeChemicalSensing",TokushimaUniversity,Tokushima770-8506,Japan.‡GraduateSchoolofLifeScience,HokkaidoUniversity,Kita-ku,Sapporo001-0021,Japan.§DepartmentofChemistry,Biology,andEnvironmentalScience,FacultyofScience,NaraWomen’sUniversity,Kitauoyanishi-machi,Nara630-8506,Japan.SupportingInformationTableofContentsTableofContents............................................................S1ExperimentalSection.........................................................S2-S4References.................................................................S4-S51H-,13C{1H}-,and31P{1H}-NMRSpectra(FiguresS1-S24)..............................S6-S29ChiralHPLCChromatograms(FiguresS25-S39).....................................S30-S44–S1–

1ExperimentalSection.General.Allanaerobicand/ormoisturesensitivemanipulationswerecarriedoutwithstandardSchlenktechniquesunderpredriednitrogenorwithgloveboxtechniquesunderprepurifiedargon.1HNMR(at400MHz)and13CNMR(at101MHz)chemicalshiftsarereportedinppmdownfieldofinternaltetramethylsilane.31PNMR(at162MHz)chemicalshiftsareexternallyreferencedto85%H3PO4.Tetrahydrofuran,benzene,and1,4-dioxaneweredistilledfrombenzophenone-ketylundernitrogenpriortouse.DMFwasdistilledfromCaH2undervacuumpriortouse.Chloroform-dwasdistilledfromP2O5undervacuumpriortouse.Diferrocenylphosphine,1(R)-2-diphenylphosphino-2'-[(trifluoromethanesulfonyl)oxy]-1,1'-binaphthyl((R)-2),2PdCl2(cod),31,1-dibromotridecene,4Pd(PPh3)4,5Pd(dba)2,62-bromo-1,3-butadienes(4a7and4b8),4-chlorophenyltriflates(8b),9and[RhCl(coe)2]210werepreparedasreported.Alltheotherchemicalswereobtainedfromcommercialsourcesandusedasreceivedunlessotherwisenoted.2-Diferrocenylphosphino-2'-diphenylphosphino-1,1'-binaphthyl(FcPh-Binap;1).ADMF(40mL)solutionofNiCl2(dppe)(0.22g,0.43mmol)anddiferrocenylphosphine(2.60g,6.39mmol)wasstirredat100°Cfor1hundernitrogen.Tothiswasaddedasolutionof(R)-2-diphenylphosphino-2'-[(trifluoromethanesulfonyl)oxy]-1,1'-binaphthyl((R)-2;2.50g,4.26mmol)andDABCO(0.96g,8.5mmol)inDMF(45mL)bymeansofcannulatransferandthesolutionwasstirredat100°Cfor60h.Thesolutionwasevaporatedtodrynessat80°C.Adark-redresiduewasdissolvedinbenzene(30mL)andthesolutionwasfilteredthroughashortpadofsilicagel.Thesilicagelpadwaswashedwithasmallamountofbenzeneandthecombinedsolutionwasevaporatedtodrynessunderreducedpressure.Theorangeresiduewaspurifiedbysilicagelchromatography(withhexane/chloroform=2/1)togive1asanorangesolid.Yield:1.86g(2.22mmol;52%).1HNMR(CDCl3):d3.43(s,5H),3.49-3.52(m,1H),3.96-3.99(m,1H),4.12(s,5H),4.18-4.20(m,1H),4.22-4.26(m,3H),4.64-4.66(m,1H),4.69-4.71(m,1H),6.50(d,J=8.5Hz,1H),6.72(t,J=7.7Hz,1H),7.02-7.07(m,5H),7.12-7.15(m,1H),7.24(d,J=8.2Hz,2H),7.36-7.52(m,5H),7.57-7.65(m,3H),7.70(d,J=8.2Hz,1H),7.74(d,J=8.6Hz,1H),7.90(d,J=8.0Hz,1H),7.96(d,J=8.6Hz,1H).31P{1H}NMR(CDCl3):d–35.0(d,J=41.5Hz),–14.0(d,J=41.5Hz).Assignmentofthe13C{1H}-NMRresonancescouldnotbemadeduetothecomplicated13C-31Pcouplingsaswellastheoverlapofthesignals.The13C{1H}-NMRspectrumofthiscompoundisattachedtothisdocument(FigureS2).Anal.CalcdforC52H40Fe2P2:C,74.48;H,4.81.Found:C,74.57;H,4.80.ESI-HRMSCalcdforC52H41Fe2P2(M+1):839.1382.Found:839.1366.ThechiralHPLCanalysisofthiscompoundrevealedthatitsenantiomericpuritywas48%eeduetopartialracemizationduringthecouplingreaction(FigureS25).Theenantiomericresolutionofscalemic1wasachievedbychiralHPLC.Amongthechiralcolumnsexamined,ChiralpakIAshowedthemosteffectiveseparationofthetwoenantiomers.Undertheanalysisconditions(columnlength:250mm;columni.d.:4.6mm;eluent:hexane/2-propanol=500/1;flowrate:1.0mL/min),(S)-1and(R)-1weredetectedat12.4minand16.6min,respectively,andtheresolutionfactor(Rs)forthisanalysiswas2.6(FigureS25).ThechiralHPLCresolutionofscalemic1couldbeconductedonasemi-macroscaleaswell.Duetothelowsolubilityofthecompound,dichloromethanewasusedasaco-solventforthesemi-macroscaleHPLC(ChiralpakIA;columnlength:250mm;columni.d.:20mm;eluent:hexane/2-propanol/dichloromethane=500/1/10;flowrate:3.0mL/min),and(S)-1and(R)-1wereobtainedinenantiomericallypureforms.[a]18D=+113.4(c0.20,CHCl3;R-enantiomer),[a]18D=–110.7(c0.14,CHCl3;S-enantiomer).PdCl2[(S)-FcPh-Binap]((S)-3).InanNMRtube,amixtureofPdCl2(cod)(6.8mg,24µmol)and(S)-1(20mg,24µmol)wasdissolvedinCDCl3(0.8mL),andthereactionwasmonitoredbythe1H-and31P-NMRmeasurements.Thereactioncompletedwithinafewminutes.Allthevolatileswereremovedundervacuum,andthedarkredresiduewasdissolvedinchloroform.ThesolutionwasfilteredthroughapadofCeliteandtheslowdiffusionofhexaneintothefilteredsolutiontogivedarkredprismsofthetitlecompound.Thecrystalscontainedcocrystallizedchloroformmolecules.Thesolvent-freecomplexwasobtainedbyprolongedevacuationat50°C.Yield:22mg(22µmol;90%).1HNMR(CDCl3):d3.00(br,1H),3.17(br,1H),3.31(br,1H),3.96(br,1H),4.07(br,1H),4.15(s,5H),4.47(br,1H),4.67(s,5H),4.70(br,1H),6.16(br,1H),6.27(d,J=8.5Hz,1H),6.65(br,2H),6.82-6.84(m,2H),6.89-6.98(m,2H),7.06(t,J=7.5Hz,1H),7.41-7.55(m,7H),7.64-7.72(m,6H),9.89(dd,J=12.0and8.9Hz,1H).31PNMR(CDCl3):d14.4(d,J=3.8Hz),26.1(d,J=3.8Hz).Assignmentofthe13C{1H}-NMRresonancescouldnotbemadeduetothecomplicated13C-31Pcouplingsaswellastheoverlapofthesignals.The13C{1H}-NMRspectrumofthiscompoundisattachedto–S2–

2thisdocument(FigureS5).[a]18D=–302.4(c0.36,CHCl3).Anal.CalcdforC52H40Cl2Fe2P2Pd:C,61.48;H,3.97.Found:C,61.70;H,4.10.3-Bromo-1,3-pentadecadiene(4c).ToaTHFsuspensionofvinylzincchloride,preparedfromdryZnCl2(5.5g,40.4mmol)andvinylmagnesiumchloride(1.46MinTHF,25mL,36.5mmol)inadditionalTHF(50mL),wasaddedasolutionof1,1-dibromotridecene(12.4g,36.5mmol)andPd(PPh3)4(850mg,736µmol)inTHF(50mL)dropwiseat0°Cbycannulatransfer.Aftertheaddition,themixturewasstirredat0°Cuntilcompleteconsumptionof1,1-dibromotridecene(checkedbyGC).Themixturewasdilutedwithhexaneandfiltered.Afterremovingthesolventsunderreducedpressure,theresiduewasredissolvedinhexaneandfilteredthroughapadofCelite.Thefiltratewasevaporated,andtheresidualoilwaspurifiedbycolumnchromatographyonsilicagel(withhexane)followedbyvacuum-transfertogive4casacolorlessoil.Yield:7.03g,(67%yield).1HNMR(CDCl3):d0.88(t,J=6.9Hz,3H),1.26(m,16H),1.40-1.47(m,2H),2.31(q,J=7.3Hz,2H),5.15(d,J=10.6Hz,1H),5.52(d,J=16.3,1H),5.98(t,J=7.1Hz,1H),6.31(dd,J=10.4and13.4Hz,1H).13C{1H}NMR(CDCl3):d14.1,22.7,28.4,29.29,29.36,29.45,29.57,29.64,29.66,31.6,31.9,117.1,125.8,135.3,135.9.Anal.CalcdforC15H27Br:C,62.71;H,9.47.Found:C,62.35;H,9.61.EI-HRMSCalcdforC15H27Br:286.1296.Found:286.1292.GeneralProcedureforPalladium-CatalyzedAsymmetricSynthesisofAxiallyChiralAllenes.Thereactionwascarriedoutaccordingtothereportedprocedure.11ThereactionconditionsandtheresultsaresummarizedinTable1.AmixtureofPd(dba)2(4.3mg,7.5µmol),chiralbisphosphine(8.2µmol),and2-bromo-1,3-butadiene4(0.15mmol)wasdissolvedinTHF(1.5mL),andthesolutionwasaddedtoamixtureofpronucleophile5(0.25mmol)andanappropriatebase(0.25mmol)inTHF(1mL).Themixturewasstirredat40°Cfor24h,thenfilteredthroughashortpadofAl2O3toremovetheprecipitatedinorganicsalts.ThealuminapadwaswashedwithsmallamountofEt2Othreetimesandthecombinedsolutionwasevaporatedtodrynessunderreducedpressure.Theorange-yellowresiduewaschromatographedonAl2O3togiveallene6inpureform.Thecharacterizationdataofallenicproducts6arelistedbelow.(R)-Diethyl2-Phenyl-2-(4-phenylbuta-2,3-dienyl)propane-1,3-dioate(6ax).Thisisaknowncompoundandits1H-NMRdataareconsistentwiththosereportedpreviously.12[a]13D=–131(c0.25,CHCl3;forthesampleof81%ee).(R)-Diethyl2-Acetamido-2-(4-phenyl-2,3-butadienyl)propane-1,3-dioate(6ay).Thisisaknowncompoundandits1H-NMRdataareconsistentwiththosereportedpreviously.11[a]15D=–137(c0.80,CHCl3;forthesampleof86%ee).(R)-Diethyl2-Acetamido-2-(4-cyclohexyl-2,3-butadienyl)propane-1,3-dioate(6by).1HNMR(CDCl3):d1.00-1.28(m,11H),1.61-1.64(m,1H),1.69-1.71(m,4H),1.87-1.95(m,1H),2.03(s,3H),3.02(dd,J=7.7and2.4Hz,2H),4.19-4.29(m,4H),4.83-4.89(m,1H),5.02-5.07(m,1H),6.79(br,1H).13CNMR(CDCl3):d13.9,14.0,23.0,25.9,26.0,32.88,32.93,37.0,62.47,62.52,66.4,84.7,97.1,167.6,167.7,168.8,204.7.ESI-HRMSCalcdforC19H29NO5Na(M+Na):374.1943.Found:374.1951.[a]13D=–43(c0.76,CHCl3;forthesampleof88%ee).(R)-2-(2,3-Pentadecadienyl)-1,3-benzodithiole-1,1,3,3-tetraoxide(6cz).1HNMR(CDCl3):d0.88(t,J=6.9Hz,3H),1.25-1.33(m,16H),1.39-1.46(m,2H),2.03-2.09(m,2H),2.96-3.00(m,2H),4.53(t,J=7.0Hz,1H),5.29-5.40(m,2H),7.90-7.94(m,2H),8.00-8.05(m,2H).13CNMR(CDCl3):d14.1,22.7,22.9,28.5,29.1,29.2,29.36,29.44,29.61,29.64,29.7,31.9,73.2,83.7,95.2,122.6(2C),135.2,135.7,137.7(2C),204.9.Anal.CalcdforC22H32O4S2:C,62.23;H,7.60.Found:C,62.33;H,7.55.ESI-HRMSCalcdforC22H32O4S2Na:447.1640(M+Na).Found:447.1635.[a]25D=–46(c0.89,CHCl3forthesampleof86%ee).GeneralProcedureforPalladium-CatalyzedIntermolecularAsymmetricHeckReactionof2,3-Dihydrofuran.AmixtureofPd(OAc)2(2.4mg,11µmol)and(R)-chiralphosphine(22µmol)inbenzene(2mL)wasstirredfor30minat50°C.Tothiswereaddedaryltriflate8(0.32mmol),2,3-dihydrofuran(7;112mg,1.6mmol),andethyldiisopropylamine(124mg,0.96mmol),thenthehomogeneousmixturewasstirredat50°Cfor72h.Aftercooledtoroomtemperature,thesolutionwasdilutedwithhexane(ca.30mL).Theprecipitatewasremovedbyfiltration,andthefiltratewasconcentratedunderreducedpressure.Theresiduewaspassedthroughashortpadofsilicagel(withhexane/ethylacetate=10/1),andtheclearsolutionwas–S3–

3concentrated.TheGCanalysisofthiscrudemixtureshowedcompleteconsumptionofaryltriflate8.Theproductdistribution(9/10ratio)wasdeterminedbythe1H-NMRanalysisofthecrudemixture.Asmallportionofthecrudemixture(ca.10%involume)wassubjectedtosilicagelchromatography(hexane/ethylacetate=10/1)toseparateisomericproducts9and10,ofwhichenantiomericpuritywasdeterminedbythechiralHPLCanalysis.Theremainingcrudemixturewasdissolvedinbenzene(2mL),andRhCl(PPh3)3(25mg;27µmol)wasaddedtothesolution.Thesolutionwasplacedunderhydrogenusingaballoon,thenstirredfor3hatroomtemperature.Thesolutionwasconcentratedunderreducedpressure,andtheresiduewaspurifiedbysilicagelchromatography(hexane/ethylacetate=10/1)togive11,ofwhichenantiomericpuritywasdeterminedbythechiralHPLCanalysis.Alltheproductsobtainedhereareknowncompoundandtheir1H-NMRdataareconsistentwiththosereportedpreviously(9a,13-159b,13,159c,1510a,13,14,16,1710b,1310c,16,1711a,14,1811b,18and11c18).Rhodium-CatalyzedAsymmetric1,4-AdditionofPhenylboronicAcidto2-cyclohexenone.Asolutionof[RhCl(coe)2]2(4.5mg,6.3μmol)andchiralphosphine(13μmol)indioxane(1mL)wasstirredatroomtemperaturefor1hundernitrogen.TothiswasaddedaqueousKOH(1.25M,0.1mL,0.13mmol),andthesolutionwasstirredfor5min.Phenylboronicacid(91.4mg,0.75mmol)and2-cyclohexenone(24mg,0.25mmol)wasaddedtothesolution.Afterstirredfor24hat50°C,themixturewasfilteredthroughashortpadofsilicageltoremoveprecipitatedinorganicsalts.ThesilicagelpadwaswashedwithasmallamountofEt2Othreetimes,andthecombinedsolutionwasevaporatedtodrynessunderreducedpressure.Theorange-yellowresiduewaspurifiedbysilicagelchromatographytogive2-phenylcyclohexanone.Thespectraldataoftheproductwasconsistentwiththosereportedpreviously.19RemarksontheX-rayCrystallography.CCDC2060069[(R)-1]:Thelevel-BalertinthecheckCIFreportofthisstructureisattributabletotheslightdisorderoftheCpring(atC27andC28)inoneoftheferrocenylgroups.CCDC2060082[(S)-3]:ThealertBofthisstructureisascribedtothedisorderedphenylring(C47-C52),whichwasrefinedisotropically.References.(1)Baxter,S.G.;Collins,R.L.;Cowley,A.H.;Sena,S.F.Ferrocenyl-SubstitutedPhospheniumCationsandPhosphideAnions.Inorg.Chem.1983,22,3475-3479.(2)(a)Kurz,L.;Lee,G.;Morgans,Jr.,D.;Waldyke,M.J.;Ward,T.StereospecificFunctionalizationof(R)-(–)-1,1'-Bi-2-naphtholTriflate.TetrahedronLett.1990,31,6321-6324.(b)Uozumi,Y.;Hayashi,T.CatalyticAsymmetricSynthesisofOpticallyActive2-AlkanolsviaHydrosilylationof1-AlkeneswithaChiralMonophosphine-PalladiumCatalyst.J.Am.Chem.Soc.1991,113,9887-9888.(c)Uozumi,Y.;Takahashi,A.;Lee,S.-Y.;Hayashi,T.SynthesisofOpticallyActive2-(Diarylphosphino)-1,1'-binaphthyls,EfficientChiralMonodentatePhosphineLigands.J.Org.Chem.1993,58,1945-1948.(3)Drew,D.;Doyle,J.R.Cyclic-DiolefinComplexesofPlatinumandPalladium.Inorg.Synth.1972,13,47-55.(4)Sugiyama,S.;Honda,M.;Komiri,T.StereochemistryoftheFourDiastereomersofPhytosphingosine.LiebigsAnn.Chem.1990,1069-1078.(5)Coulson,D.R.Tetrakis(triphenylphosphine)palladium(0).Inorg.Synth.1972,13,121-124.(6)Ukai,T.;Kawazura,H.;Ishii,Y.;Bonnet,J.J.;Ibers,J.A.ChemistryofDibenzylideneacetone-Palladium(0)complexes:I.NovelTris(dibenzylideneacetone)dipalladium(solvent)ComplexesandTheirReactionswithQuinones.J.Organomet.Chem.1974,65,253-266.(7)Ogasawara,M.;Ikeda,H.;Hayashi,T.p-Allylpalladium-MediatedCatalyticSynthesisofFunctionalizedAllenes.Angew.Chem.,Int.Ed.2000,39,1042-1044.(8)Ogasawara,M.;Ge,Y.;Uetake,K.;Fan,L.;Takahashi,T.PreparationofMultisubstitutedAllenesfromAllylsilanes.J.Org.Chem.2005,70,3871-3876.–S4–

4(9)Wolfe,J.P.;Buchwald,S.L.Palladium-CatalyzedAminationofArylHalidesandArylTriflates:N-Hexyl-2-methyl-4-methoxyanilineandN-Methyl-N-(4-chlorphenyl)aniline.Org.Synth.2002,78,23-35.(10)VanderEnt,A.;Onderdelinden,A.L.Chlorobis(cyclooctene)rhodium(I)anddi-µ-chlorobis[bis(cryclooctene)iridium](I)complexes.Inorg.Synth.1973,14,92-95.(11)Ogasawara,M.;Ikeda,H.;Nagano,T.;Hayashi,T.Palladium-CatalyzedAsymmetricSynthesisofAxiallyChiralAllenes:ASynergisticEffectofDibenzalacetoneonHighEnantioselectivity.J.Am.Chem.Soc.2001,123,2089-2090.(12)Hu,H.;Ichiryu,H.;Seki,N.;Nakajima,K.;Ohki,Y.;Ogasawara,M.Synthesis,Characterization,andApplicationofSegphosDerivativeHavingDiferrocenylphosphino-DonorMoieties.Organometallics2020,39,788-792.(13)Ozawa,F.;Kubo,A.;Hayashi,T.CatalyticAsymmetricArylationof2,3-DihydrofuranwithArylTriflates.J.Am.Chem.Soc.1991,113,1417-1419.(14)Ozawa,F.;Kubo,A.;Matsumoto,Y.;Hayashi,T.;Nishioka,E.;Yanagi,K.;Moriguchi,K.Palladium-CatalyzedAsymmetricArylationof2,3-DihydrofuranwithPhenylTriflate.ANovelAsymmetricCatalysisInvolvingaKineticResolutionProcess.Organometallics1993,12,4188-4196.(15)Penn,L.;Shpruhman,A.;Gelman,D.Enantio-andRegioselectiveHeck-TypeReactionofArylboronicAcidswith2,3-Dihydrofuran.J.Org.Chem.2007,72,3875-3879.(16)Wu,C.;Zhou,J.AsymmetricIntermolecularHeckReactionofArylHalides.J.Am.Chem.Soc.2014,136,650-652.(17)Mazloomi,Z.;Magre,M.;DelValle,E.;Pericàs,M.A.;Pàmies,O.;vanLeeuwen,P.W.N.M.;Diégueza,M.Synthesis,ApplicationandKineticStudiesofChiralPhosphite-OxazolinePalladiumComplexesasActiveandSelectiveCatalystsinIntermolecularHeckReactions.Adv.Synth.Catal.2018,360,1650-1664.(18)Sun,S.;Yang,Y.Zhao,R.;Zhang,D.;Liu,L.Site-andEnantiodifferentiatingC(sp3)−HOxidationEnablesAsymmetricAccesstoStructurallyandStereochemicallyDiverseSaturatedCyclicEthers.J.Am.Chem.Soc.2020,142,19346-19353.(19)Takaya,Y.;Ogasawara,M.;Hayashi,T.;Sakai,M.;Miyaura,N.Rhodium-CatalyzedAsymmetric1,4-AdditionofAryl-andAlkenylboronicAcidstoEnones.J.Am.Chem.Soc.1998,120,5579-5580.–S5–

5PFc2PPh211H-NMRinCDClat400MHz3FigureS1.1H-NMRSpectrumofFcPh-Binap(1)inCDCl3at400MHz.–S6–

6PFc2PPh2113C-NMRinCDClat101MHz3FigureS2.13C{1H}-NMRSpectrumofFcPh-Binap(1)inCDCl3at101MHz.–S7–

7PFc2PPh2131P-NMRinCDClat162MHz3FigureS3.31P{1H}-NMRSpectrumofFcPh-Binap(1)inCDCl3at162MHz.–S8–

8Fc2PPdCl2PPh231H-NMRinCDClat400MHz3FigureS4.1H-NMRSpectrumofPdCl2(FcPh-Binap)(3)inCDCl3at400MHz.–S9–

9Fc2PPdCl2PPh2313C-NMRinCDClat101MHz3FigureS5.13C{1H}-NMRSpectrumofPdCl2(FcPh-Binap)(3)inCDCl3at101MHz.–S10–

10Fc2PPdCl2PPh2331P-NMRinCDClat162MHz3FigureS6.31P{1H}-NMRSpectrumofPdCl2(FcPh-Binap)(3)inCDCl3at162MHz.–S11–

11nCH11234cBr1H-NMRinCDClat400MHz3FigureS7.1H-NMRSpectrumof4cinCDCl3at400MHz.–S12–

12nCH11234cBr13C-NMRinCDClat101MHz3FigureS8.13C{1H}-NMRSpectrumof4cinCDCl3at101MHz.–S13–

13Ph•CO2EtCO2EtPh6ax1H-NMRinCDClat400MHz3FigureS9.1H-NMRSpectrumof6axinCDCl3at400MHz.–S14–

14Ph•CO2EtCO2EtNHAc6ay1H-NMRinCDClat400MHz3FigureS10.1H-NMRSpectrumof6ayinCDCl3at400MHz.–S15–

15Cy•CO2EtCO2EtNHAc6by1H-NMRinCDClat400MHz3FigureS11.1H-NMRSpectrumof6byinCDCl3at400MHz.–S16–

16Cy•CO2EtCO2EtNHAc6by13C-NMRinCDClat101MHz3FigureS12.13C{1H}-NMRSpectrumof6byinCDCl3at101MHz.–S17–

17nC11H23•SO26czO2S1H-NMRinCDClat400MHz3FigureS13.1H-NMRSpectrumof6czinCDCl3at400MHz.–S18–

18nC11H23•SO26czO2S13C-NMRinCDClat101MHz3FigureS14.13C{1H}-NMRSpectrumof6czinCDCl3at101MHz.–S19–

199aPhO1H-NMRinCDClat400MHz3FigureS15.1H-NMRSpectrumof9ainCDCl3at400MHz.–S20–

2010aPhO1H-NMRinCDClat400MHz3FigureS16.1H-NMRSpectrumof10ainCDCl3at400MHz.–S21–

2111aPhO1H-NMRinCDClat400MHz3FigureS17.1H-NMRSpectrumof11ainCDCl3at400MHz.–S22–

229bOp-C6H4Cl1H-NMRinCDClat400MHz3FigureS18.1H-NMRSpectrumof9binCDCl3at400MHz.–S23–

2310bOp-C6H4Cl1H-NMRinCDClat400MHz3FigureS19.1H-NMRSpectrumof10binCDCl3at400MHz.–S24–

2411bOp-C6H4Cl1H-NMRinCDClat400MHz3FigureS20.1H-NMRSpectrumof11binCDCl3at400MHz.–S25–

259cOp-C6H4Me1H-NMRinCDClat400MHz3FigureS21.1H-NMRSpectrumof9cinCDCl3at400MHz.–S26–

2610cOp-C6H4Me1H-NMRinCDClat400MHz3FigureS22.1H-NMRSpectrumof10cinCDCl3at400MHz.–S27–

2711cOp-C6H4Me1H-NMRinCDClat400MHz3FigureS23.1H-NMRSpectrumof11cinCDCl3at400MHz.–S28–

28OPh1H-NMRinCDClat400MHz3FigureS24.1H-NMRSpectrumof3-PhenylcyclohexanoneinCDCl3at400MHz.–S29–

29FigureS25.ChiralHPLCAnalysisof1(Scheme1);racemic(top);reactionproduct(2nd);(R)-1(3rd);(S)-1(bottom);ChiralpakIA;eluent:hexane/iPrOH=500/1;flowrate:1.0mL/min.PFc2PPh2rac-1;FcPh-BinapPFc2PPh2(R)-1;FcPh-Binap(48%ee)#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(S)-isomer112.87518639712689226.06938.51410572.0462.3562(R)-isomer117.00052861484293273.93161.486765N/A2.380PFc2PPh2(R)-1;FcPh-BinapPFc2PPh2(S)-1;FcPh-Binap–S30–

30FigureS26.ChiralHPLCAnalysisof6ax(Table1,entries1and2);racemic(top);with(R)-Binap(middle);with(R)-FcPh-Binap(1)(bottom);ChiralpakAS-H;eluent:hexane/iPrOH=500/1;flowrate:0.5mL/min.Ph•CO2EtCO2Et6axPhracemic34%ee(R)-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(R)-isomer126.2252765639526227767.02474.02315311.5531.6432(S)-isomer131.175136073269204132.97625.9771128N/AN/A81%ee(R)-FcPh-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(R)-isomer125.8081449805914429990.44092.69716371.6441.5402(S)-isomer130.8331532493113689.5607.3031188N/AN/A–S31–

31FigureS27.ChiralHPLCAnalysisof6ay(Table1,entries3and4);racemic(top);with(R)-Binap(middle);with(R)-FcPh-Binap(1)(bottom);ChiralcelOJ-H;eluent:hexane/iPrOH=20/1;flowrate:1.0mL/min.Ph•CO2EtCO2Et6ayNHAcracemic82%ee(R)-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(S)-isomer132.9504818836330909.23912.19012631.6521.6272(R)-isomer140.1834733838623836190.76187.8101004N/A1.67686%ee(R)-FcPh-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(S)-isomer133.3175949843391536.8378.98712011.5611.6202(R)-isomer140.3838107355339649593.16391.013953N/A1.688–S32–

32FigureS28.ChiralHPLCAnalysisof6by(Table1,entries5and6);racemic(top);with(R)-Binap(middle);with(R)-FcPh-Binap(1)(bottom);ChiralpakIA;eluent:hexane/iPrOH=20/1;flowrate:1.0mL/min.Cy•CO2EtCO2Et6ayNHAcracemic54%ee(R)-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(R)-isomer113.450450119919640976.77877.48685203.2071.1552(S)-isomer115.38313613945706723.22222.5149667N/A1.10088%ee(R)-FcPh-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(R)-isomer113.458941547434909194.18593.55163273.2451.1782(S)-isomer115.567581275240645.8156.4499890N/A1.036–S33–

33FigureS29.ChiralHPLCAnalysisof6cz(Table1,entries7and8);racemic(top);with(R)-Binap(middle);with(R)-FcPh-Binap(1)(bottom);ChiralpakIC;eluent:hexane/iPrOH=20/1;flowrate:1.0mL/min.nC11H23•SO26czO2Sracemic46%ee(R)-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(S)-isomer116.0001116549941376926.95737.67585094.3411.1662(R)-isomer119.9673025348568448573.04362.3254920N/A1.53886%ee(R)-FcPh-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(S)-isomer115.47528173941103937.19212.43088413.9381.0382(R)-isomer119.1083635857977771792.80887.5704113N/A1.704–S34–

34FigureS30.ChiralHPLCAnalysisof9a(Table2,entries1and2);racemic(top);with(R)-Binap(middle);with(R)-FcPh-Binap(1)(bottom);ChiralcelOB-H;eluent:hexane/iPrOH=50/1;flowrate:1.0mL/min.PhOracemic70%ee(R)-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(S)-isomer17.6084596584847215.26817.525152563.1701.2212(R)-isomer18.458255102722811684.73282.47513484N/A1.25495%ee(R)-FcPh-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(S)-isomer17.608271207296252.7463.493158932.7341.2002(R)-isomer18.358960613781846897.25496.50711735N/A1.512–S35–

35FigureS31.ChiralHPLCAnalysisof10a(Table2,entries1and2);racemic(top);with(R)-Binap(bottom);ChiralcelOB-H;eluent:hexane/iPrOH=50/1;flowrate:1.0mL/min.PhOracemic46%ee(R)-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(S)-isomer111.41743714297572.90077.325144878.9811.2492(R)-isomer115.3921625187227.10022.67514679N/A1.136–S36–

36FigureS32.ChiralHPLCAnalysisof11a(Table2,entries1and2);racemic(top);with(R)-Binap(middle);with(R)-FcPh-Binap(1)(bottom);ChiralcelOB-H;eluent:hexane/iPrOH=50/1;flowrate:1.0mL/min.PhOracemic64%ee(R)-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(S)-isomer110.29210842367692718.18827.214124497.5261.3152(R)-isomer114.058487705820575381.81272.7867849N/A1.62995%ee(R)-FcPh-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(S)-isomer110.208150653118662.7285.239113887.2891.1422(R)-isomer114.050537180521464097.27294.7616945N/A1.621–S37–

37FigureS33.ChiralHPLCAnalysisof9b(Table2,entries3and4);racemic(top);with(R)-Binap(middle);with(R)-FcPh-Binap(1)(bottom);ChiralcelOB-H;eluent:hexane/iPrOH=50/1;flowrate:0.5mL/min.Op-C6H4Clracemic70%ee(R)-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(R)-isomer113.3081126200571055284.95086.959163305.5221.1852(S)-isomer115.817199525110655615.05013.04116383N/A1.09092%ee(R)-FcPh-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(R)-isomer113.100870400455985995.99996.518164725.4831.1852(S)-isomer115.525362796201964.0013.48216833N/A1.090–S38–

38FigureS34.ChiralHPLCAnalysisof10b(Table2,entries3and4);racemic(top);with(R)-Binap(middle);with(R)-FcPh-Binap(1)(bottom);ChiralcelOB-H;eluent:hexane/iPrOH=50/1;flowrate:0.5mL/min.Op-C6H4Clracemic(S)-41%ee(R)-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(S)-isomer115.642610064532970170.23474.578168736.3651.1642(R)-isomer119.033258549911238629.76625.42216830N/A1.272(R)-72%ee(R)-FcPh-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(S)-isomer115.49210698516069514.13916.874178206.2101.1442(R)-isomer118.683649669729901285.86183.12617410N/A1.176–S39–

39FigureS35.ChiralHPLCAnalysisof11b(Table2,entries3and4);racemic(top);with(R)-Binap(middle);with(R)-FcPh-Binap(1)(bottom);ChiralcelOB-H;eluent:hexane/iPrOH=50/1;flowrate:1.0mL/min.Op-C6H4Clracemic58%ee(R)-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(S)-isomer15.725322038343670421.06828.143142894.6851.3312(R)-isomer16.85812064958111502878.93271.8578732N/A1.31591%ee(R)-FcPh-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(S)-isomer15.750276722408924.5556.774159725.3471.2232(R)-isomer16.958579789956275095.44593.22610533N/A1.214–S40–

40FigureS36.ChiralHPLCAnalysisof9c(Table2,entries5and6);racemic(top);with(R)-Binap(middle);with(R)-FcPh-Binap(1)(bottom);ChiralcelOB-H;eluent:hexane/iPrOH=50/1;flowrate:1.0mL/min.Op-C6H4Meracemic55%ee(R)-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(S)-isomer116.558550919725769922.57827.557136663.8051.1662(R)-isomer119.0331889189367744477.42272.44310644N/A1.28394%ee(R)-FcPh-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(S)-isomer18.992259988223893.1594.000138393.105N/A2(R)-isomer110.067797090253734796.84196.00010742N/A1.303–S41–

41FigureS37.ChiralHPLCAnalysisof10c(Table2,entries5and6);racemic(top);with(R)-Binap(middle);with(R)-FcPh-Binap(1)(bottom);ChiralcelOB-H;eluent:hexane/iPrOH=50/1;flowrate:1.0mL/min.Op-C6H4Meracemic(S)-25%ee(R)-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(S)-isomer111.408208371712381762.61671.329109828.2741.3792(R)-isomer115.95812440654976937.38428.6719151N/A1.150(R)-57%ee(R)-FcPh-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(S)-isomer113.017153437879921.49028.685133879.6771.2112(R)-isomer118.4005605532187578.51071.31512230N/A1.198–S42–

42FigureS38.ChiralHPLCAnalysisof11c(Table2,entries5and6);racemic(top);with(R)-Binap(middle);with(R)-FcPh-Binap(1)(bottom);ChiralcelOB-H;eluent:hexane/iPrOH=50/1;flowrate:1.0mL/min.Op-C6H4Meracemic55%ee(R)-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(S)-isomer19.4009956547670722.47733.582121277.5891.1912(R)-isomer112.967343391715171177.52366.4187447N/A1.15994%ee(R)-FcPh-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(S)-isomer112.833740944390543.2306.197104476.4421.1852(R)-isomer117.6422219605959118896.77093.8035035N/A1.710–S43–

43FigureS39.ChiralHPLCAnalysisof3-phenylcycloexanone(Scheme2);racemic(top);with(R)-Binap(middle);with(R)-FcPh-Binap(1)(bottom);ChiralpakAD-H;eluent:hexane/iPrOH=100/1;flowrate:1.0mL/min.OPhracemic99%ee(R)-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(S)-isomer113.1083118112530.4270.81168132.5361.6172(R)-isomer115.358727496815311099.57399.1892885N/A3.19687%ee(R)-FcPh-Binap#peaknameCHtR[min]area[µV•sec]height[µV]area%height%NTPresolutionsymmetrycoefficient1(S)-isomer113.1507629027646.7169.06458063.0371.8882(R)-isomer115.62510596882773093.28490.9364382N/A2.438–S44–