1. p. 251

2. Alkenes & Alkynes Prepapration of alkenes 1. Dehydrohalogenation
2. Dehydration

3. Alkenes & Alkynes Reactions of alkenes & alkynes
A. Electrophilic Additions
Hydrohalogenation
i. alkenes
ii. alkynes
2. Halogenation
Halohydrins
4. Hydration

4. Alkenes & Alkynes Reactions of alkenes & alkynes
A. Electrophilic Additions
Hydrohalogenation
i. alkenes
ii. alkynes

5. Electrophilic addition of Br2 to an alkene

6. p. 217

7. p. 218

8. Alkenes & Alkynes Reactions of alkenes & alkynes
A. Electrophilic Additions
2. Halogenation
i. alkenes (working backwards)

9. Alkenes & Alkynes Reactions of alkenes & alkynes
A. Electrophilic Additions
Halohydrins
i. alkenes

10. Alkenes & Alkynes Reactions of alkenes & alkynes
A. Electrophilic Additions
Halohydrins
ii. alkynes

11. Alkenes & Alkynes Reactions of alkenes & alkynes
A. Electrophilic Additions
4. Hydration
i. alkenes
a. acid catalyzed

12. Alkenes & Alkynes Reactions of alkenes & alkynes
A. Electrophilic Additions
4. Hydration
i. alkenes
a. hydroboration & oxidation

13. p. 223

14. d + d - d +
Figure 7.4: Mechanism of alkene hydroboration. The reaction occurs in a single step in which both C–H and C–B bonds form at the same time and on the same face of the double bond. The lower energy, more rapidly formed transition state is the one with less steric crowding, leading to non-Markovnikov regiochemistry. d -
Fig. 7-4, p. 225

15. Jmol

16. Alkenes & Alkynes Reactions of alkenes & alkynes
A. Electrophilic Additions
4. Hydration
i. alkynes
a. acid catalyzed

17. Alkenes & Alkynes Reactions of alkenes & alkynes
A. Electrophilic Additions
4. Hydration
i. alkynes
b. oxymercuration

18. Alkenes & Alkynes Reactions of alkenes & alkynes
A. Electrophilic Additions
4. Hydration
i. alkynes
a. hydroboration & oxidation

19. Alkenes & Alkynes Reactions of alkenes & alkynes B. Reductions
i. Catalytic hydrogenation

20. Alkenes & Alkynes Reactions of alkenes & alkynes B. Reductions
i. Catalytic hydrogenation
a. Complete reduction

21. Alkenes & Alkynes Reactions of alkenes & alkynes B. Reductions
i. Catalytic hydrogenation
b. Lindlar’s catalyst (partial reduction)

22. Alkenes & Alkynes Reactions of alkenes & alkynes C. Reductions
ii. Dissolving metal reduction (partial reduction)

24. ep ep !

25. Alkenes & Alkynes
Reactions of alkenes & alkynes
C. Alkyne alkylation

26. Figure 8.19
A comparison of alkyl, vinylic, and acetylide anions. The acetylide anion, with sp hybridization, has more s character and is more stable. Electrostatic potential maps show that placing the negative charge closer to the carbon nucleus makes carbon appear less negative (red).
Fig. 8-19, p. 292

27. Alkenes & Alkynes
Reactions of alkenes & alkynes
D. Carbene addition

28. Figure 7. 6: The structure of dichlorocarbene
Figure 7.6: The structure of dichlorocarbene. Electrostatic potential maps show how the positive region (blue) coincides with the empty p orbital in both dichlorocarbene and a carbocation (CH3+). The negative region (red) in the dichlorocarbene map coincides with the lone-pair electrons.
Fig. 7-6, p. 228

29. Carbenes

30. Alkenes & Alkynes Reactions of alkenes & alkynes E. Oxidations
Introduction

31. Alkenes & Alkynes Reactions of alkenes & alkynes E. Oxidations
1. epoxidation
Peracids (RCO3H)

32. Epoxide formation through reaction of peracids

33. Alkenes & Alkynes Reactions of alkenes & alkynes E. Oxidations
1. epoxidation
ii. via halohydrins

34. The Nobel Prize in Chemistry 2001
"for their work on chirally catalysed hydrogenation reactions"
"for his work on chirally catalysed oxidation reactions"
William S. Knowles
Ryoji Noyori
K. Barry Sharpless

35. Thalidomide
Racemic thalidomide prescribed for morning sickness (1956 – 1961)
(R)-enantiomer is an antiemetic
(S)-enantiomer is a teratogen

36. Sharpless epoxidation
(CH3)3COOH

37. Knowles Asymmetric Reduction

38. Alkenes & Alkynes Reactions of alkenes & alkynes E. Oxidations
2. dihydroxylation
i. osmium tetraoxide

39. Alkenes & Alkynes Reactions of alkenes & alkynes E. Oxidations
2. dihydroxylation
ii. from epoxides

40. Alkenes & Alkynes Reactions of alkenes & alkynes E. Oxidations
2. Dihydroxylation
Application : Synthesis

41. Alkenes & Alkynes Reactions of alkenes & alkynes E. Oxidations
3. oxidative cleavage
i. ozonolysis

42. p. 237

43. Alkenes & Alkynes Reactions of alkenes & alkynes E. Oxidations
3. oxidative cleavage
i. ozonolysis

44. Alkenes & Alkynes Reactions of alkenes & alkynes E. Oxidations
3. oxidative cleavage
ii. permanganate

45. Alkenes & Alkynes Reactions of alkenes & alkynes E. Oxidations
3. oxidative cleavage
iii. from diols

46. Alkenes & Alkynes Reactions of alkenes & alkynes F. Conjugated Dienes
Introduction

47. Figure 8.12
Two p orbitals combine to form two π molecular orbitals. Both electrons occupy the low-energy, bonding orbital, leading to a net lowering of energy and formation of a stable bond. The asterisk on ψ2* indicates an antibonding orbital.
Fig. 8-12, p. 281

48. Figure 8.13
Four π molecular orbitals in buta-1,3-diene. Note that the number of nodes between nuclei increases as the energy level of the orbital increases.
Fig. 8-13, p. 282

49. Figure 8.14
Electrostatic potential maps of buta-1,3-diene (conjugated) and penta-1,4-diene (nonconjugated) show additional electron density (red) in the central C–C bond of buta-1,3-diene, corresponding to partial double-bond character.
Fig. 8-14, p. 282

50. Alkenes & Alkynes Reactions of alkenes & alkynes F. Conjugated Dienes
1. Addition of HX

51. Reaction energy diagram for addition of HBr to butadiene

52. Alkenes & Alkynes Reactions of alkenes & alkynes F. Conjugated Dienes
2. The Diels-Alder reaction
Introduction
a. the overall reaction
b. history
c. nature of the diene and dienophile
d. the molecular orbital picture
e. conformation of the diene

53. Alkenes & Alkynes Reactions of alkenes & alkynes F. Conjugated Dienes
2. The Diels-Alder reaction
Introduction
a. the overall reaction

54. Alkenes & Alkynes Reactions of alkenes & alkynes F. Conjugated Dienes
2. The Diels-Alder reaction
Introduction
b. history
Albrecht reaction
Liebigs 1906, 348, 31.
Staudinger, H.; Bruson, H. A.
Liebigs 1926 , 446 , 97.
Diels, O.; Alder, K.
Liebigs. 1928, 460, 98.
Nobel Prize 1950

55. "for their discovery and development of the diene synthesis "
The Nobel Prize in Chemistry 1950
"for their discovery and development of the diene synthesis "
Otto Paul Hermann Diels
Kurt Alder

56. Alkenes & Alkynes Reactions of alkenes & alkynes F. Conjugated Dienes
2. The Diels-Alder reaction
Introduction
c. nature of the diene and dienophile

57. p. 286

58. Alkenes & Alkynes Reactions of alkenes & alkynes F. Conjugated Dienes
2. The Diels-Alder reaction
Introduction
d. the molecular orbital picture

59. Alkenes & Alkynes Reactions of alkenes & alkynes F. Conjugated Dienes
2. The Diels-Alder reaction
Introduction
e. the diene conformation

60. Alkenes & Alkynes Reactions of alkenes & alkynes F. Conjugated Dienes
2. The Diels-Alder reaction
Stereochemistry (Alder’s Endo Rule)

61. Alkenes & Alkynes Reactions of alkenes & alkynes F. Conjugated Dienes
2. The Diels-Alder reaction
Regiochemistry (The Ortho Rule)

62. Alkenes & Alkynes Reactions of alkenes & alkynes F. Conjugated Dienes
2. The Diels-Alder reaction
Regiochemistry (The Para Rule)

63. Figure 8.17
Electrostatic potential maps of ethylene, propenal, and propenenitrile show that electron-withdrawing groups make the double-bond carbons less electron-rich (less red).
Fig. 8-17, p. 287