碳-杂重键的加成反应.pptVIP

完成下列反应： 比较有光学活性的下列两个化合物，用　Ｈ２１８Ｏ在酸催化下水解的反应产物，用反应机制加以说明。 5.3 Addition to C,O multiple bonds Base catalyzed Step 1. Step 2. Mechanism No matter which species attack first, the rate-determining step is usually the one involving Nu attack! Acid catalyzed Step 1. Step 2. Competed procedure: Substitution Step 3. Step 4. Step 2. Step 1. When A, B are H, R, Ar, the substrate is an aldehyde or ketone, these almost undergo addition! For carboxylic acids and their derivatives (B = OH, OR, NH2, X, etc), the substitution is major procedure! Activity Electronic effect CCl3-CH=O + HOH CCl3-CH(OH)2 Steric effect Nucleophilicity Stereochemistry + LiAlH4 88% 12% LiAl(s-BuO)3H 7% 93% ether LiAlH4 H2O + 75% 25% Aldol condensation Base-catalyzed -H+ -H2O 烯醇化 亲核加成 H+ -H+ Acid-catalyzed Claisen-Schemidt reaction H2O-C2H5OH NaOH 88 % -93% Thorpe Reaction Knoevenagel reaction eg 1. eg 2. eg 3. 制备各种类型的α,β-不饱和化合物. Mannich reaction Primary or secondary amine Active hydrogen compounds H+转移 Acid catalyzed 制备α,β-不饱和醛酮 Wittg reaction Ylide Ph3P + CH3X Ph3P+-CH3X- C6H5Li Ph3P+-CH2- Ph3P + XCH2COOC2H5 Ph3P+-CH2COOC2H5 X- K2CO3 Mechanism 内鏻盐 Reformatsky Reaction Darzens Reaction α,β-环氧酸酯 * CH2 生成醛 CHR 生成酮 H+ Mechanism -CO2 Benzoin Condensation 安息香 X. Linghu, J. S. Johnson, Angew. Chem., 2003, 115, 2638 acceptor(donor) donor(acceptor) 交错Benzoin Condensation Breslow Intermediate Cannizzaro Reaction (Disproportionation) NaOH C2H5OH ~50oC + H+ 反应机理 交错的Cannizzaro 反应： 季戊四醇 羧酸衍生物与亲核试剂的反应 减小 反应活性： ——加成-消除历程 酯的水解 BAC2 Or H+ R’具有手性时，构型保持 AAC2 AAL1 R’具有手性时，外消旋化 Claisen Condensation Strong base 思考：为什么要选用强碱催化？ Dieckmann Condensation