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

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Contents

Preface

xi

I. FUNCTIONAL GROUP MODIFICATIONS

1. Chemical Oxidations

I.

II.

III.

IV.

V.

VI.

VII.

VIII.

IX.

X.

XI.

2.

Chromium Trioxide Oxidation

Periodate-Permanganate Cleavage of Olefins

Free Radical Oxidation of an Allylic Position

Epoxidation of Olefins

Baeyer-Villiger Oxidation of Ketones

Lead Tetraacetate Oxidation of Cycloalkanols

Photolytic Conversion of Cyclohexane to Cyclohexanone Oxime

Oxidation of Ethers to Esters

Partial Oxidation of an Aliphatic Side Chain

Bisdecarboxylation with Lead Tetraacetate

Oxidation with Selenium Dioxide

References

3

5

7

8

9

11

11

12

13

14

15

16

Hydride and Related Reductions

I.

II.

III.

IV.

Reduction by Lithium Aluminum Hydride

Mixed Hydride Reduction

Reduction with Iridium-Containing Catalysts

Reduction of Conjugated Alkenes with Chromium (H) Sulfate

References

18

20

22

23

24

3. Dissolving Metal Reductions

I.

II.

III.

IV.

V.

Reduction by Lithium-Amine

Reduction by Lithium-Ethylenediamine

Reduction of a,/MJnsaturated Ketones by Lithium-Ammonia

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

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

References

. . . .

25

26

27

28

29

30

VI

CONTENTS

4. Hydroboration

I. Hydroboration of Olefins as a Route to Alcohols

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

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

References

32

35

37

38

5. Catalytic Hydrogenation

I.

II.

III.

IV.

V.

Hydrogenation over Platinum Catalyst

Low-Pressure Hydrogenation of Phenols over Rhodium Catalysts

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

3-Isoquinuclidone from/7-Aminobenzoic Acid

Homogeneous Catalytic Hydrogenation

References

39

40

41

42

43

44

6. The Introduction of Halogen

I.

II.

III.

IV.

V.

Halides from Alcohols by Triphenylphosphine��Carbon Tetrahalide

Halides from Alcohols and Phenols by Triphenylphosphine Dihalide

Allylic and Benzylic Bromination with W-Bromosuccinimide

a-Bromination of Ketones and Dehydrobromination

Stereospecific Synthesis of /ra/w-4-Halocyclohexanols

References

45

46

48

49

51

52

7. Miscellaneous Elimination, Substitution, and Addition Reactions

I.

II.

III.

IV.

V.

VI.

VII.

VIII.

IX.

X.

XI.

XII.

Methylenecyclohexane by Pyrolysis of an Amine Oxide

The Wolff-Kishner Reduction

Dehydration of 2-Decalol

Boron Trifluoride Catalyzed Hydrolysis of Nitriles

Bridged Sulfides by Addition of Sulfur Dichloride to Dienes

Methylation by Diazomethane

Oxymercuration: A Convenient Route to Markovnikov Hydration of Olefins .

Esterification of Tertiary Alcohols

Ketalization

Half-EsterificationofaDiol

Substitution on Ferrocene

Demethylation of Aryl Methyl Ethers by Boron Tribromide

References

. . .

54

55

56

56

57

58

60

62

63

64

65

66

67

CONTENTS

II.

VlI

SKELETAL MODIFICATIONS

8. The Diels-Alder Reaction

I.

II.

III.

IV.

V.

9.

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

...........

Reactions with Butadiene

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

Catalysis by Aluminum Chloride

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

Generation of Dienes from Diones

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

Reactions with Cyclopentadiene

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

References

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

71

72

74

75

77

79

Enamines as Intermediates

I.

II.

III.

IV.

V.

Preparation of the Morpholine Enamine of Cyclohexanone

.........

Acylation of Enamines

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

Enamines as Michael Addition Reagents

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

Reactions of Enamines with j3-Propiolactone

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

Reactions of Enamines with Acrolein

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

References

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

80

81

82

83

84

86

10. Enolate Ions as Intermediates

I.

II.

III.

IV.

V.

VI.

VII.

Ketones as Enolates: Car bethoxylation of Cyclic Ketones

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

Methylsulfinyl Carbanion as a Route to Methyl Ketones

Cyclization with Diethyl Malonate

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

Carboxylations with Magnesium Methyl Carbonate (MMC)

Alkylation of j3-Ketoesters

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

The Robinson Annelation Reaction

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

References

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

.........

.......

..........

.........

87

90

92

96

97

99

101

103

1 1 . The Wittig Reaction

I.

II.

III.

IV.

V.

Benzyl-Containing Ylides

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

Alkyl Ylides Requiring ?-Butyl Lithium

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

Methylsulfinyl Carbanion in the Generation of Ylides

..........

The Wittig Reaction Catalyzed by Ethylene Oxide

...........

Cyclopropylidene Derivatives via the Wittig Reaction

..........

References

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

104

105

106

107

108

110

1 2 . Reactions of Trialkylbor anes

I.

II.

III.

IV.

Trialkylcarbinols from Trialkylboranes and Carbon Monoxide

........

Dialkylketones from Trialkylboranes and Carbon Monoxide-Water

......

The Reaction of Trialkylboranes with Methyl Vinyl Ketone and Acrolein

.....

The Reaction of Trialkylboranes with Ethyl Bromoacetate

.........

References

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

Ill

112

114

115

115

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