D.H. Ripin, D.A. Evans pKa's of Inorganic and Oxo-Acids ...

1 Ripin, Evans *Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various & SULFONIC ACIDSPEROXIDESH2 OpKa(DMSO)(DMSO)pKaH2OH2 OpKa(DMSO) pKa's of Inorganic and ( )( )( )( )CF3SO3H-14( )( )(15)( )( )(32)(DMSO)(CF3)2 CHOHCF3CH2 OHt-BuOHMeOHHOHcis-CO2 Htrans-CO2 HHR= , , , , , + , (OH)3 Inorganic ACIDSChem 206 SubstrateSubstrate++ , + (CH3)3N+ (CH3)3N+ , ( )( )PROTONATED SPECIESCARBOXYLIC ACIDS( )( )( )( )( )( ) ( )2-napthol( )( )( ) & HYDROXAMIC (NH) ( )pKa H2 OOOHRPhPhNOHNHPhOHN+OOHO+HHMeNOHPhOMeOOH XMeO+MeN+OOHPhOHOHPhPhCH3 OHO+HHMeSOHOOPhSOHOSOHMeMeO+ Ripin, Evans *Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various (12) (estimate) pKa's of Nitrogen AcidsH2O (DMSO)Chem 206 SubstrateSubstrateSubstratepKaSubstrateD ABCODBUEt3N+Hi-Pr2N+H2i-Pr2 NHEtN+H3 TMS2 NHN+H4NH3 TMP(41)(36 THF))(37)(30)( ) ( )( )PhN+H3Ph2N+ + ( )H2NN+H3 HON+ + (PPTS) ( )+ + ( )PhN+(Me) ( )R= ( )+ , ( , )( ) , ( )Proton , (--, )++( )12+( )( )( )(44)NCNH2( )( )1,2,3 triazole( )R= HCH3 PhCF3NH2 (urea)

2 OEt( )( )( )( )( )( ) ( )Ac2NH( )Cl, ( )( )( ) (NH) ( )( )PhSO2 NHNH2( )( )( )PhNHNHPh( )AMIDES & CARBAMATESPROTONATED NITROGENAMINESPhSO2NH2 MeSO2NH2CF3SO2NH2( )( ) ( ) ( )PhCN+H-10 MeSO2 NHPh( )IMIDESSULFONAMIDEHYRDAZONES,- IDES, & -INESHYDROXAMIC ACIDAMIDINESHETEROCYCLESPROTONATED HETEROCYCLESR= Me( )Ph( )pKa(DMSO)H2OH2O (DMSO)pKapKa(DMSO)H2 OGUANIDINIUM,N+N+NNHNHMeMeMeMeO2 NNO2NO2NH3 NHHNHNHMe2 NNHRRHH3N++NH3NH3NH3 NHOOBnON+HN+H2 HNHNNNHH2 NNNNNHRNH2 ONHONHEtPhNHONHONHOOOONHONHPhOHPhMe2 NNMe2N+H2 MeNNH2 ONHNH2 PhNSO2 PhNH2R26(THF) Ripin, ~36H2*Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various (DMSO)SubstrateSubstrateSubstratepKaSubs trateAMIDESHYDROCARBONSpKa(DMSO)H2OH2O (DMSO)pKapKa(DMSO)H2 OCH4CH2=CHCH3 PhHCH2=CH2 PhCH3Ph2CH2Ph3CH(56)(44)(43)( )( )(Me)3CH53(Me) ( )XC6H4CH3X=p-CNp-NO2p-COPh( )( )( )( )( )( )1520X= HPhSPhCOCH3SO2Ph( )( )( )( )( )( )( )( )( )X= HCH3 COCH3 COPhCO2 EtCNOMeNPh2( )N+Me3NO2 SPhOPhSO2 PhSePh( )( )( )( )( )( )( )( )( )( )( )( )( )( )( )X=HOMeNMe2 BrCN( )( )( )( )( )n=87654( )( )( )( )( )( )( )( )( )( )( )( )( )( )( )( )( )( )( )

3 ( )( )FPhKETONESESTERSn[ (THF)] pKa's of CH bonds in Hydrocarbons and Carbonyl CompoundsMeMeMeMeMeOXOEtEtSi-Pri-PrOOMet -BuPhXPhi-PrOOLiOOPhMeOXOOOOOMeMet-BuOOM et-BuOOPhEtOON+Me3 OEtOMeOOOMeMeOOOMeOSN+Me3 OEt2 NPhOMe2 NMe2 NOSPhNOCNMe2 NMeSOMeMe2 NOChem Ripin, Evans11( )( ) 710-11 PhSHBuSH*Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.( )( )Me3S+=OSULFONIUM( )( )(33)( )( )( )i-PrMeR=SULFIMIDES & SULFOXIMINESX= HPhSPh( )( )( )( )( )(33)SOPhPhHX=( )SULFOXIDES( )PhSCH=CHCH2 SPh( )( )( )( )t-Bui-PrEtMeR=RSCH2CN( )( )( )CNCO2 MePhX=( )( )(PrS)3CH( )(PhS)3CH( )PhSCHPh2( )(PhS)2 CHPh( )MeSCH2SO2Ph( )( )( )( )( )( )( )( )( )POPh2SO2CF3SO2 PhSPhNO2 COPhCOCH3 CNPhX=PhSCH2 XSULFIDES( )( )( )( )( )( )H2O (DMSO)SubstrateSubstrateSubstratepKaSubs trateHETERO-AROMATICSNITRILESpKa(DMSO)H2 OH2O (DMSO)pKapKa(DMSO)H2OX=HCH3 PhCOPhCONR2CO2 EtCNOPhN+Me3 SPhSO2Ph( )( )( )( )( )( )( )( )( )( )( )

4 SULFONESX= HCH3t-BuPhCH=CH2CH=CHPhCCHCOPhCCPhCOMeOP hN+Me3 CNNO2 SMeSPhSO2 PhPPh2( )( )( )( )( )( )( )( )( )( )( )( )( )( )( )( )( )( )( )(PhSO2)2CH2Me( )( )( )( )( )( ) pKa's of CH bonds at Nitrile, Heteroaromatic, and Sulfur Substituted CarbonNCXNPhPhNNPhPhN+OPhPhSO-SOOPhXSOPh SCHPh2 OOOMeMeSSSHSSPhSXOSOXSOCHPh2 PhXMeSNTsPhSRPhMeNTsOSONMeMePhPhSMeN+Me2 OSONTsCH2 ClPhPhS+CH2 PhMeMeCF3 SMeOOSOOi-PrCF3 EtSEtOOCF3 SOOChem 206( )IMINESn( )( )( )( )( )76543n=( )( )( )( )( )( )( )( )CH2 COPhCH2SO2 PhCH2 SPhCH2 BnCH2 PhCHMe2CH2 MeCH3R=RNO2 NITRO( )( )Ph2 PCH2SO2 PhPh2 PCH2 PPh2( )CN( )SPhX=PHOSPHINES( )( )( )( )( )SiMe3 ClCO2 EtCNPhX=PHOSPONATES & PHOSPHINE OXIDES( )( )( )( )Ph3P+CH2 CNPh3P+CH2 COPhPh3P+i-PrPh3P+ + +H3-14P+H4 PHOSPHONIUM( )( )( )( )( )CONEt2CO2 EtCOPhSO2 PhCNX=Me3N+CH2 XAMMONIUM( )( )PhOCH2SO2Ph( )PhOCH2CN( )MeOCH2SO2Ph(49)CH3 OPhSELENIDESETHERS( )PhSeCH=CHCH2 SePh( )PhSeCH2Ph ( )(PhSe)2CH2( )PhSeCHPh2( )H2O (DMSO)D.

5 H. Ripin, D. A. EvansSubstrateSubstrateSubstratepKapKa(D MSO)H2OH2O (DMSO)pKapKa's of CH bonds at Heteroatom Substituted Carbon & ReferencesREFERENCESDMSO:JACS 97, 7007 (1975)JACS 97, 7160 (1975)JACS 97, 442 (1975)JACS 105, 6188 (1983)JOC 41, 1883 (1976)JOC 41, 1885 (1976)JOC 41, 2786 (1976)JOC 41, 2508 (1976)JOC 42, 1817 (1977)JOC 42, 321 (1977)JOC 42, 326 (1977)JOC 43, 3113 (1978)JOC 43, 3095 (1978)JOC 43, 1764 (1978)JOC 45, 3325 (1980)JOC 45, 3305 (1980)JOC 45, 3884 (1980)JOC 46, 4327 (1981)JOC 46, 632 (1981)JOC 47, 3224 (1982)JOC 47, 2504 (1982)Acc. Chem. Res. 21, 456 (1988)Unpublished results of F.

6 BordwellWater:Advanced Org. Chem., 3rd Ed. J. March (1985)Unpublished results of W. P. JencksTHF:JACS 110, 5705 (1988) 10*Values <0 for H2O and DMSO, and values >14 for water and >35 for DMSO were extrapolated using various methods.(EtO)2 PXOPh2 POXO2 NPhPhNPhPhSePhOOPhMeOChem 206 Oxime ethers are ~ 10 pka units less acidic than their ketone counterpartsStreitwieser, JOC 1991, 56, 1989