Chapter 19. Organic Chemistry. Carbonyl Compounds III. Reactions at the a-carbon. 4 th Edition Paula Yurkanis Bruice

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1 Organic Chemistry 4 th Edition Paula Yurkanis Bruice Chapter 19 Carbonyl Compounds III Reactions at the a-carbon Disampaikan oleh: Dr. Sri Handayani 2013 Irene Lee Case Western Reserve University Cleveland, OH 2004, Prentice Hall

2 The a-hydrogen Is Acidic the anion is stabilized by resonance A carbon acid is a compound with a relatively acidic hydrogen bonded to an sp 3 -hybridized carbon

3

4 Esters Are Less Acidic Than Aldehydes and Ketones The electrons are not as readily delocalized

5 In these compounds, the electrons left behind from deprotonation can be delocalized onto a more electronegative atom

6 The acidity of the a-hydrogens is attributed to charge stabilization by resonance

7 Keto Enol Tautomerism

8 The enol tautomer can be stabilized by intramolecular hydrogen bonding In phenol, the enol tautomer is aromatic

9

10

11 An Enol Is a Better Nucleophile Than an Alkene Carbonyl compounds that form enol undergo substitution reactions at the a-carbon: an a-substitution reaction

12 An Acid-Catalyzed a-substitution Reaction

13 A Base-Catalyzed a-substitution Reaction

14 An Enolate Is an Ambident Nucleophile Reaction at the C or O site depends on the electrophile and on the reaction condition Protonation occurs preferentially on the O site Otherwise, the C site is likely the nucleophile

15 Acid-Catalyzed Halogenation Under acidic conditions, one a-hydrogen is substituted for a bromine

16 Base-Promoted Halogenation Under basic conditions, all the a-hydrogens are substituted for bromines

17 Conversion of a Methyl Ketone to a Carboxylic Acid

18 Halogenation of the a-carbon of Carboxylic Acids

19 When the a-carbon is halogenated, it becomes electrophilic An E2 elimination will occur if a bulky base is used

20 Using LDA to Form an Enolate

21 Alkylation of the a-carbon of Carbonyl Compounds

22 Two different products can be formed if the ketone is not symmetrical

23 The less substituted a-carbon can be alkylated if + Li Bu -

24 Enamine Reacts with Electrophiles

25 The alkylation step is an S N 2 reaction

26 Direct alkylation of a carbonyl compound yields several products In contrast, alkylation of an aldehyde or a ketone using an enamine intermediate yields the monoalkylated product

27 Aldehydes and ketones can be acylated via an enamine intermediate

28 The Michael Addition

29

30 Mechanism of the Michael Reaction

31 The Stork Enamine Reaction Enamines are used in place of enolates in Michael reactions

32 One molecule of a carbonyl compound acts as a nucleophile and the other carbonyl compound acts as an electrophile

33

34 Ketones are less susceptible than aldehydes to attack by nucleophiles

35 An aldol addition product loses water to form an aldol condensation product

36

37 The Mixed Aldol Addition

38 One product will be formed if one of the carbonyl compounds does not have any a-hydrogen

39 Primarily one product can be formed by using LDA to deprotonate one of the carbonyl compounds

40 Condensation of Two Ester Molecules

41

42 The reaction can be driven to completion by removal of a proton from the b-keto ester The Claisen condensation requires an ester with two a-hydrogens and an equivalent amount of base

43 The Mixed Claisen Condensation

44 Because of the difference in the acidities of the a-hydrogens in the two carbonyl compounds, primarily one product is obtained

45

46 Intramolecular Aldol Additions

47

48 The Robinson Annulation

49 Decarboxylation of 3-Oxocarboxylic Acids

50 Acid catalyzes the intramolecular transfer of the proton

51 A malonic ester synthesis forms a carboxylic acid with two more carbon atoms than the alkyl halide

52

53 Preparation of Carboxylic Acids with Two Substituents Bonded to the a-carbon

54 Synthesis of Methyl Ketone by Acetoacetic Ester Synthesis

55

56 Designing a Synthesis to Make New Carbon Carbon Bonds

57 Preparation of the Ester

58 A Biological Aldol Condensation

59 A Biological Claisen Condensation

60

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