5.2 碳-碳重键的加成反应.ppt

5.2.1 Electrophilic addition to C,C multiple bonds 5.2.2 Nucleophilic addition to C,C multiple bonds 5.2.3 Concerted addition to C,C multiple bonds The reaction is general-acid, not special-acid catalyzed, implying the rate determining proton transfer from acid to the double bond. Cabocation intermediates is involved. Markovnikov’s rule:give the more stable cabocations. EDG increase the reactivity of a double bond, while EWG decrease it. Cabocations are prone to rearrange. Nium mediate mechanism Anti addition Attack by Cl+, I+,RS+,Hg+ is similar to that by Br+ A bromonium ion is not formed where the carbocation can be stabilized in other ways! 思考题： * 5.2 Addition to C,C multiple bonds 碳-碳重键加成反应类型： （1）亲电加成反应 如： （2）亲核加成 如： （3）自由基加成 如： （4）环加成 如： Ⅰ. Carbocation mechanism Direction: The more stable carbocation form preferentially Caution: Carbocation rearrangement! 5.2.1 Electrophilic addition to C,C multiple bonds Four types of mechanism + Y- nonstereospecific Ⅱ. Ion pair mechanism Syn addition Ⅲ. Termolecular mechanism YE EY Anti addition Ⅳ.Nium reaction mechanism minor contributing structure Stereospecificity: Anti addition (一) Addition of HW 1.与HX Reactivity: HIHBrHClHF 2. 与H2O，ROH, H2SO4, RCOOH HX ROH HOSO2OH HOH ArOH RCOOH ?强酸催化，易重排 (二) Addition of X2 ﹖ Reactivity: double bond （三） Oxymercuration-Reduction ?反应选择性好，不易重排 A bridged mercurinium: three-center/two-electron bond The electronegativity tell you which one is E+. （四） Other electrophilic reagents Addition to conjugated dienes ﹖ 5.2.2 Nucleophilic addition to C,C multiple bonds EWG: CHO, COR, COOR, CONH2, CN, NO2, SOR, SO2R H+ 互变异构 H （一）Conjugate addition Michael Addition donors acceptors Michael addition Robinson reaction （二）Nucleophilic Additon to C,C triple bond ﹖ 5.2.3 Concerted addition to C,C multiple bonds A syn addition mechanism （一） Catalytic hydrogenation 烯烃的加氢 催化氢化 二亚胺加氢（环状络合物中间体加氢） 异相催化氢化（吸附加氢）