1. Ketones and Aldehydes Properties Nomenclature Preparation Reactions Synthesis

2. Carbonyl Functional Groups

3. Large Dipole Controls Properties and Reactivity

4. Boiling Points Dipole-Dipole Interactions

5. Adrogenic/Anabolic Steroids

6. Anabolic Steroids

7. IUPAC Nomenclature Ketones

9. IUPAC Nomenclature Aldehydes

10. Classical Aldehyde Nomenclature

12. Preparation of Ketones and Aldehydes Friedel-Crafts Acylation (ketones) Gatterman-Koch Formylation (aldehydes) Hydration of Alkynes (ketones with oxymercuration, aldehydes with hydroboration) Ozonolysis of Alkenes (aldehydes and ketones depending on substitution) 1,3-Dithiane alkylations (aldehydes and ketones) Reduction of acids, acid chlorides and nitriles Gilman Reaction (ketones)

13. Friedel-Crafts Acylation

14. Isoflavones Highly Sought After Natural Products

16. Acylation occurs ortho to OH

17. Gatterman-Koch Formylation

18. Oxymercuration Hydration Markovnikov

19. Hydroboration Hydration Anti-Markovnikov

20. Ozonolysis Alkene Cleavage

21. Gilman Reagent with Acid Chlorides

22. DIBAH Diisobutyl Aluminum Hydride

23. Nucleophilic Addition Reactions: Strong Nucleophiles

24. Carbonyl Reactivity

25. Cyanohydrin Formation

26. Nucleophilic Addition Reactions: Weak Nucleophiles

27. Acetal Formation

28. Acetal Mechanism

29. Propose a Mechanism

30. Use of Ethylene Glycol to Protect Ketones and Aldehydes

31. Synthesis

32. Aldehydes React Preferentially

33. Imine Formation

34. Imines and Enamines

36. Imine Derivatives

37. Wolff-Kishner Reduction

38. Mechanism from Hydrazone

39. Deoxygenation

40. Enamine Mechanism (same as imine mech. until last step)

41. Wittig Reaction: C=O into C=C

42. Ylide Synthesis

44. Mechanism

46. Pure Alkene is Formed in Wittig Rxn

47. (Methoxymethylene)-triphenylphosphorane an Aldehyde Prep

48. Propose a Sequence of Steps…

49. Provide a Mechanism

51. Conjugate Addition to ,  -Unsaturated C=O groups

52. 1,2- vs. 1,4-Addition

53. Gilman Reagents add 1,4

54. Synthesis

55. Carry Out Conjugate Addition 1st

56. MCAD Deficiency, a Genetic Disease Children with any of these enzyme deficiencies have a significant risk (20%) of death during the first, clinical episode of hypoglycemia (low blood glucose). Those patients affected show episodes of acute, life-threatening attacks that are symptomatically consistent with Reye’s Syndrome and sometimes misdiagnosed as S.I.D.S. The most common of these in-born errors is MCAD Deficiency. (Medium Chain Acyl-CoA Dehydrogenase) ~1/50 Caucasians carry the gene.

57. MCAD Enzyme (MCAD) is one of the enzymes involved in mitochondrial fatty acid  -oxidation, which fuels hepatic ketogenesis, a major source of energy once hepatic glycogen stores become depleted during prolonged fasting and periods of higher energy demands. Typically, a previously healthy child with MCAD deficiency presents with hypoketotic hypoglycemia, vomiting, liver dysfunction, skeletal muscle weakness and lethargy triggered by a common illness. On average, this occurs between 3 and 24 months of age.

58. Ackee Fruit (Bligia Sapida) from Jamaica Ingestion of the unripe seeds from the fruit of the Jamaican Ackee tree causes a disruption of the dehydrogenase enzymes needed to metabolize fatty acids. This “vomiting sickness” is a result of the enzyme inhibitor Hypoglycin A.

59. (R)(-) MCPA is the Toxic Metabolite of Hypoglycin-A

60. Wittig Approach to Both Enantiomers

61. Wittig Approach to (S)(+)-MCPA Start with (R)(-) Epichlorohydrin S N 2 on 1 o Alkyl Chloride?

62. Wittig Sequence Affords (S) (Methylenecyclopropyl)methanol

63. Homologation to (S)(-)-MCPA

64. Approach to (R)-(+)-MCPA Same Wittig Approach with Ylide Opening the Epoxide First?