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1、SupportingInformationAsymmetricHydrocyanationofHydrazonesCatalyzedbyinsituFormedO-silylatedBINOL-Phosphate:AConvenientAccesstoVersatileα-HydrazinoAcidsAlexandruZamfirandSvetlanaB.Tsogoeva*DepartmentofChemistryandPharmacy,ChairofOrganicChemistryI,Universityo
2、fErlangen-Nuremberg,Henkestrasse42,91054Erlangen,GermanyFax:(+49)-(0)9131-85-26865E-mail:tsogoeva@chemie.uni-erlangen.de1.ExperimentalSection12.SpectralDataofProducts31133.HandCSpectraofProducts74.SpectraConcerningtheReactionMechanism235.HPLCMeasurements291
3、.ExperimentalSectionGeneralRemarks:Commercialproductswereusedwithoutfurtherpurification.Hydrazonesweresynthesizedfromcommercialavailablehydrazinesandaldehydes,purchasedfromSigma-AldrichCo.orAcrosOrganics.Allsolventsusedwerepreviouslydriedusingappropriatemet
4、hods.ColumnchromatographywasperformedonAcrossilicagel60ÅandTLConMacherey-®113NagelALUGramSILG/UV254plates.HNMRandCNMRspectrawererecordedonBrukerAvance400(400MHz;2001)orBrukerAvance300(300MHz;2001)usingthesolventasinternalstandard.Massspectra(m/z,relativeint
5、ensity(%))wererecordedwithaShimadzuAXIMAConfidence-MALDITimeofFlight(TOF)massspectrometeroraMicromassZabSpec(FAB)system.HPLCmeasurementswererecordedonAgilent1200Seriessystem.Thesynthesisofcatalystswasbasedonknownprocedures.Forsynthesisof3,3`-BINOLderivates,
6、see:Wipf,P.Jung,J.-K.J.Org.Chem.2000,65,6319.Forsynthesisofbinaphtylphosphatessee:M.Yamamaka,J.Itoh,K.Fuchibe,T.Akiyama,J.Am.Chem.Soc.2007,129,6756.Allcatalystshavepreviouslybeenreportedexcept9and10.GeneralProcedurefortheHydrocyanationofHydrazones:Catalyst(
7、0.0068mmol,5mol%)wasaddedinonebatchtoasolutionofhydrazone(0.1356tmmol)inCH2Cl2(3mL)andBuOH(0.027mmol,20mol%)at-10°C.Afterstirringfor20min,TMSCN(0.271mmol,2equiv)wasaddedtothereactionmixtureandthestirringcontinuedfor72hat-10°C.Theconstantcoolingwasachievedwi
8、ththeuseofacryostat.Themixturewasdirectlyappliedonthesilicagelcolumnandpurifiedbychromatography(EtOAc:DCM:PE=4:1:5).-1-ConversionoftheProduct2toα-Hydrazinoacid5:NO2HNNH2HNHN6NHClxHClOCOOHCNreflux,8h52(
