北大Ch 8 碳正离子.ppt

? 形成环状聚合物 Organic Synthesis b.Crossed condensations Base-catalyzed crossed aldol condensation Anthocyanidin Anthocyanin Acid-catalyzed crossed reaction with one enolized carbonyl group Organic Synthesis c. Reactions between ketones and acid chlorides or anhydrides 1,3-二酮 Anhydrous Condition Lewis acid 80% 质子的离去 Organic Synthesis The different result with unsymmetrical ketones between the acid- and base-catalyzed process. 如何解释产物选择性的差异? Organic Synthesis d. Reactions of 2-methylpyridine and related compounds Formation of nitrogen-analogue of an enol 质子的离去 “烯醇化” Organic Synthesis 2-, 4-methyl quinoline Organic Synthesis Question: can not undergo the corresponding acid-catalyzed reaction, please make a reasonable explanation. The following compounds 3-methylpyridine 3-methylisoquinoline Organic Synthesis Pinacyanol (cation) 季铵盐的“烯醇化” Organic Synthesis 5. Mannich reaction 胺甲基化反应 Mannich base 70% 含活泼氢的化合物 + 甲醛 + 胺 胺甲基化 (?-氨基酮) 酸性条件 1o、2o 胺或盐 Organic Synthesis Mechanism: 亚胺的质子化 形成亲电试剂 羰基的烯醇化 形成亲核试剂 Organic Synthesis Stuctural requisites in the reactants Amine: R2NH, RNH2, NH3 1o 胺 氨 Organic Synthesis ?Aldehydes Other related Mannich reactions: ? b-Dibasic acids, b-cyano-acids, b-keto-acids,etc. ? Ketone Organic Synthesis ? 2-Methylpyridine and related compounds ? Phenols ? Furan, pyrrole, indole, and their derivatives Organic Synthesis Modifications of the Mannich reaction Pre-formed immonium salts 亚胺盐 Eschenmoser’s salt Organic Synthesis Avoids the need for an acid catalyst 避免使用酸为催化剂 Eschenmoser’s salt Organic Synthesis The applications of Mannich bases in synthesis ?Formation of a, b-unsaturated carbonyl compounds Organic Synthesis ? Replacement of the amino group Benzylic-type Mannich Base, susceptible to nucleophilic displacements SN2 substitution by nucleophiles heteroauxin Organic Synthesis Synthesis of Tryptophan Susceptible to hydrogenolysi