中国科学院大学-高等有机化学-第三章-通过取代（包括保护和脱保护）进行官能团互换-Functional Group Interconversion by Substitution, Including Protection and Deprotection.ppt

Aluminum amides Hydrolysis Alkanine solution of H2O2 3.5. Installation and Removal of Protective Groups 3.5.1. Hydroxy-Protecting Groups 3.5.1.1. Acetals as Protective Groups. THP EE MOM and MEM MEM is more stable than THP under acidic aqueous hydrolysis, But less stable than THP and MOM when treated with ZnBr2, TiCl4, (Me)2BBr, MgBr2 and TMSI. SEM SEM can be removed by TBAF, pyridinium floride, HF, MgBr2 3.5.1.2. Ethers as Protective Groups Me, t-Butyl, triphenylmethyl (Tr) Me and Tr can be introduced by halide under basic condition, while t-Butyl.. Removed under acidic condition or strong Lewis acid. DMTr, PMTri and Tr can also be removed with Ce(NH3)6(NO3)3 (CAN) Benzyl ethers: Bz, PMB, DMB Introduced by halide, phenyldiazomethane and Williamson Reaction: Benzyl ethers: Bz, PMB, DMB Cleaved by catalytic hydrogenolysis, or by electron-transfer reduction using Na/NH3 or by Lewis acids such as FeCl3 and SnCl4 or by dichlorodicyanoquinone (DDQ). 3.5.1.3. Silyl Ethers as Protective Groups TMS, TES, TBDMS, TBDPS, TPS, TIPS, TBODPS Introduced by halide or triflate Removed by hydrolytic conditions (acidic), or TBAF, methanolic NH4F, or aqueous HF, BF3, or SiF4 Hydrolytic stability of the various silyl protecting groups is in the order: TMS TES TBDMS TIPS TBDPS (Steric effect) TBODPS are more sensitive to fluoride than TBDMS and TBDPS 3.5.1.4. Esters as Protective Groups Acetates, benzoates, and pivalates, can be conveniently prepared by reaction of unhindered alcohols with acetic anhydride, benzoyl chloride, or pivaloyl chloride, respectively. Pyridine or other tertiary amines. 4-Dimethylaminopyridine (DMAP) is often usedas a catalyst. Can be removed readily by base-catalyzed hydrolysis. Trichloroethyl carbonate esters can be reductively removed with Zn. 3.5.1.5. Protective Groups for Diols Removal: Can be readily removed by aqueous acid Introduction: 3.5.2. Amino-Protecting Groups Cbz BOC Ally Carbamate 3.5.2. Amino-Protecting Groups Phthalimides Trifluo