Advanced Organic Synthesis

Advanced Organic Synthesis

METHODS AND TECHNIQUES

RICHARD S. MONSON

DEPARTMENT OF CHEMISTRY CALIFORNIA STATE COLLEGE, HAYWARD HAYWARD, CALIFORNIA

ACADEMIC PRESS New York and London

COPYRIGHT ? 1971, BY ACADEMIC PRESS, INC. ALL RIGHTS RESERVED NO PART OF THIS BOOK MAY BE REPRODUCEDIN ANY FORN BY PHOTOSTAT, MICROFILM, RETRIEVAL SYSTEM, OR ANY OTHER MEANS, WITHOUT WRITTEN PERMISSION FROM THE PUBLISHERS.

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Contents

Preface

xi

I. FUNCTIONAL GROUP MODIFICATIONS

1. Chemical Oxidations

I. Chromium Trioxide Oxidation

3

II. Periodate-Permanganate Cleavage of Olefins

5

III. Free Radical Oxidation of an Allylic Position

7

IV. Epoxidation of Olefins

8

V. Baeyer-Villiger Oxidation of Ketones

9

VI. Lead Tetraacetate Oxidation of Cycloalkanols

11

VII. Photolytic Conversion of Cyclohexane to Cyclohexanone Oxime

11

VIII. Oxidation of Ethers to Esters

12

IX. Partial Oxidation of an Aliphatic Side Chain

13

X. Bisdecarboxylation with Lead Tetraacetate

14

XI. Oxidation with Selenium Dioxide

15

References

16

2. Hydride and Related Reductions

I. Reduction by Lithium Aluminum Hydride

18

II. Mixed Hydride Reduction

20

III. Reduction with Iridium-Containing Catalysts

22

IV. Reduction of Conjugated Alkenes with Chromium (H) Sulfate

23

References

24

3. Dissolving Metal Reductions

I. Reduction by Lithium-Amine

25

II. Reduction by Lithium-Ethylenediamine

26

III. Reduction of a,/MJnsaturated Ketones by Lithium-Ammonia

27

IV. Reduction of a,/9-Unsaturated Ketones in Hexamethylphosphoric Triamide . . . . 28

V. Reduction of an a,/?-Unsaturated y-Diketone with Zinc

29

References

30

VI

CONTENTS

4. Hydroboration

I. Hydroboration of Olefins as a Route to Alcohols

32

II. Selective Hydroborations Using Bis(3-methyl-2-butyl)borane (BMB)

35

III. Purification of a Mixture of J9-10- and J1(9)-Octalins

37

References

38

5. Catalytic Hydrogenation

I. Hydrogenation over Platinum Catalyst

39

II. Low-Pressure Hydrogenation of Phenols over Rhodium Catalysts

40

III. c/j-4-Hydroxycyclohexanecarboxylic Acid from /?-Hydroxybenzoic Acid

41

IV. 3-Isoquinuclidone from/7-Aminobenzoic Acid

42

V. Homogeneous Catalytic Hydrogenation

43

References

44

6. The Introduction of Halogen

I. Halides from Alcohols by Triphenylphosphine--Carbon Tetrahalide

45

II. Halides from Alcohols and Phenols by Triphenylphosphine Dihalide

46

III. Allylic and Benzylic Bromination with W-Bromosuccinimide

48

IV. a-Bromination of Ketones and Dehydrobromination

49

V. Stereospecific Synthesis of /ra/w-4-Halocyclohexanols

51

References

52

7. Miscellaneous Elimination, Substitution, and Addition Reactions

I. Methylenecyclohexane by Pyrolysis of an Amine Oxide

54

II. The Wolff-Kishner Reduction

55

III. Dehydration of 2-Decalol

56

IV. Boron Trifluoride Catalyzed Hydrolysis of Nitriles

56

V. Bridged Sulfides by Addition of Sulfur Dichloride to Dienes

57

VI. Methylation by Diazomethane

58

VII. Oxymercuration: A Convenient Route to MarkovnikovHydration of Olefins . . . . 60

VIII. Esterification of Tertiary Alcohols

62

IX. Ketalization

63

X. Half-EsterificationofaDiol

64

XI. Substitution on Ferrocene

65

XII. Demethylation of Aryl Methyl Ethers by Boron Tribromide

66

References

67

CONTENTS

VlI

II. SKELETAL MODIFICATIONS

8. The Diels-Alder Reaction

I. 3,6-Diphenyl-4,5-cyclohexenedicarboxylic Anhydride

...........

71

II. Reactions with Butadiene

..................

72

III. Catalysis by Aluminum Chloride

................

74

IV. Generation of Dienes from Diones

................

75

V. Reactions with Cyclopentadiene

.................

77

References

.......................

79

9. Enamines as Intermediates

I. Preparation of the Morpholine Enamine of Cyclohexanone

.........

80

II. Acylation of Enamines

...................

81

III. Enamines as Michael Addition Reagents

..............

82

IV. Reactions of Enamines with j3-Propiolactone

.............

83

V. Reactions of Enamines with Acrolein

...............

84

References

.......................

86

10. Enolate Ions as Intermediates

I. Ketones as Enolates: Carbethoxylation of Cyclic Ketones

.........

87

II. Esters as Enolates: 1,4-Cyclohexanedione and Meerwein's Ester

.......

90

III. Methylsulfinyl Carbanion as a Route to Methyl Ketones

..........

92

IV. Cyclization with Diethyl Malonate

................

96

V. Carboxylations with Magnesium Methyl Carbonate (MMC)

.........

97

VI. Alkylation of j3-Ketoesters

..................

99

VII. The Robinson Annelation Reaction

................

101

References

.......................

103

1 1 . The Wittig Reaction

I. Benzyl-Containing Ylides

..................

104

II. Alkyl Ylides Requiring ?-Butyl Lithium

..............

105

III. Methylsulfinyl Carbanion in the Generation of Ylides

..........

106

IV. The Wittig Reaction Catalyzed by Ethylene Oxide

...........

107

V. Cyclopropylidene Derivatives via the Wittig Reaction

..........

108

References

.......................

110

12 . Reactions of Trialkylboranes

I. Trialkylcarbinols from Trialkylboranes and Carbon Monoxide

........

Ill

II. Dialkylketones from Trialkylboranes and Carbon Monoxide-Water

......

112

III. The Reaction of Trialkylboranes with Methyl Vinyl Ketone and Acrolein

.....

114

IV. The Reaction of Trialkylboranes with Ethyl Bromoacetate

.........

115

References

.......................

115

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