高等有机合成 全套课件.ppt

高等有机合成Advanced Organic Synthesis An extension of this method 氧化反应的概念 碳原子周围电子云密度的降低，即碳原子氧化数(氧化态，氧化值)升高的反应。 广义的概念 狭义的概念 加氧反应和/或脱氢反应。 氧化反应的分类 1. 碳原子上的氢被吸电子的基团或原子取代 2. 碳碳相联接转变成与吸电子基团或原子相联接 3. 脱氢 4. 功能团的氧化 选择性高 反应条件温和 环境友好 原料便宜易得 理想的氧化反应 ? Epoxidation reactions: --------- Oxidation of Carbon-Carbon Double Bonds Comprehensive Org. Syn., Vol. 1, 819; Vol. 7, 357, 390. Peracid Oxidation 1. Peracid Reactivity: The lower the pKa, the greater the reactivity (i.e., the better the leaving group) 2. Mechanism: 过氧酸对双键发生亲电进攻，形成环氧化合物。 3. Stereochemistry: Stereochemistry of olefin is maintained: diastereospecific. Reaction rate is insensitive to solvent polarity concerted mechanism without intermediacy of ionic intermediates. c. Less hindered face of olefin is epoxidized. 4. Chemoselectivity: --Electrophilic reagent: most nucleophilic C=C reacts fastest. --Examples: 5. Diastereoselectivity ? Endocyclic Olefins ? Exocyclic Olefins Henbest, J. Chem. Soc., Chem. Commun., 1967, 1085. ----The effective size of the reagent increases with increasing solvent polarity, i.e. the solvation shell of the reagent increases in size ---Small reagent preference: axial attack and 1,3-diaxial interactions vary with size of the reagent. ---Large reagent preference: equatorial attack and 1,2- interactions (torsional strain) are relatively invariant with the size of the reagent. Carlson, J. Org. Chem., 1967, 32, 1363. ? Allylic Alcohols (endocyclic) Henbest J. Chem. Soc., 1957, 1958; Proc.Chem. Soc, 1963, 159. ---Metal-catalyzed epoxidations of allylic alcohols Sharpless Aldrichimica Acta 1979, 12, 63. ? Allylic Alcohols (exocyclic) Vedejs and Dent., J.Am.Chem. Soc., 1989, 111, 6861. ? Acyclic Allylic Alcohols Generalizations: Eclipsed Conformations in m-CPBA Epoxidation Bisected Conformations in Metal-Catalyzed Epoxidation Examples: (continued) (continued) ? Homoallylic Alcohols (高烯丙系) --Alternative chair has two a