Enols and Enolates a Substitutions and Condensations of ：烯醇和烯醇化物一个替换和缩合反应.pptVIP

Enols and Enolatesa Substitutions and Condensations of Ketones and Aldehydes Tautomerization Accelerated in Acid a-Halogenation Reaction Occurs via Enol Tautomerization Acceleration in Base Alkylation in BaseReaction with 1o RX Using LDA as Base to form Enolate Alkylation a to C=OC-alkylation preferred Alkylation Occurs on Less Hindered Side of C=O Malonic Ester Synthesis of Carboxylic Acids H’s are unusually acidic Decarboxylation (loss of CO2) 2 Acidic a H’s, 2 Alkylations; Determine the Product of the Synthesis All b-keto acids are unstable and Decarboxylate Enamines can be Alkylated Alkylation of an Enaminea Position is Activated Complements LDA Reaction LDA vs. Enamine Reaction a-Selenation: Formation of a,b-Unsaturated Ketones Mechanism Synthesis Aldol Condensation Enolate Undergoes Nucleophilic Addition Aldol CondensationDimerization of 3-Pentanone Crossed Aldol Between 2 Different C=O Compounds Four Possible Condensation Products Crossed Aldol Condensation Dehydration of Aldol Products Predicting Aldol Dehydration Products Intramolecular Aldol Predict the Product Conjugate Addition 1,2 - vs. 1,4 - Addition Michael AdditionConjugate Addition of Enolate to a,b-Unsaturated Ketone Robinson Annulation:Michael Addition followed by Aldol Consensation * *