Amino Protecting Groups Stability氨基保护基团稳定性.pdf

http:/www.organic-chemistry.org/Amino Protecting Groups Stability Protecting group is stable under these conditions Protecting group is moderately stable/might react Protecting group is labile Fmoc-NR29-Fluorenylmethyl carbamate,FMOC amino,FMOC amine,FMOC amide H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2BOC-NR 2t-Butyl carbamate,BOC amine,BOC amino,BOC amide H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2Cbz-NR2/Z-NR2Benzyl carbamate H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2Ac-NR2Acetamide H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2 http:/www.organic-chemistry.org/Trifluoroacetamide H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2Phthalimide H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2Bn-NR2Benzylamine H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2Tr-NR2Triphenylmethylamine(Tritylamine)H2O:pH 12,100CBases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2Benzylideneamine H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2Ts-NR2p-Toluenesulfonamide,Tosylamide H2O:pH 12,100CBases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2http:/www.organic-chemistry.org/Carbonyl Protecting Groups Stability Dimethyl acetal H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl21,3-Dioxanes1,3-Dioxolanes H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl21,3-Dithianes 1,3-Dithiolanes H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2N,N-Dimethylhydrazone H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2 http:/www.organic-chemistry.org/Carboxyl Protecting Groups Stability Methyl ester H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2t-Butyl ester H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2Benzyl ester H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2S-t-Butyl ester H2O:pH 12,100CBases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl22-Alkyl-1,3-oxazoline H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2 http:/www.organic-chemistry.org/Hydroxyl Protecting Groups Stability MOM-OR Methoxymethyl ether,MOM ether H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2THP-ORTetrahydropyranyl ether,THP ether H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2t-Butyl ether H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2Allyl ether H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2Bn-OR Benzyl ether H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2 http:/www.organic-chemistry.org/TBDMS-ORt-Butyldimethylsilyl ether,TBDMS ether H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2TBDPS-OR t-Butyldiphenylsilyl ether,TBDPS ether H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2Ac-OR Acetic acid ester,Acetate ester,Acetate H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2Pv-OR Pivalic acid ester,Pivalate ester,Pivalate H2O:pH 12,100CBases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2Bz-OR Benzoic acid ester,Benzoate ester,Benzoate H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2 http:/www.organic-chemistry.org/1,2-and 1,3-diols Acetonide H2O:pH 12,100CBases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2Benzylidene acetal H2O:pH 12,100C Bases:LDA NEt3,Py t-BuOK Others:DCC SOCl2Nucleophiles:RLi RMgX RCuLi Enolates NH3,RNH2NaOCH3Electrophiles:RCOCl RCHO CH3I Others:CCl2Bu3SnH Reduction:H2/Ni H2/Rh Zn/HCl Na/NH3LiAlH4NaBH4 Oxidation:KMnO4OsO4CrO3/Py RCOOOH I2,Br2,Cl2MnO2/CH2Cl2T.W.Green,P.G.M.Wuts,Protective Groups in Organic Synthesis,Wiley-Interscience,New York,1999,207-215,716-719.