Organic Synthesis State of the Art 2005-2007

Douglass F. Taber University of Delaware

Newark, DE

WILEY A JOHN WILEY & SONS, INC., PUBLICATION

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Organic Synthesis State of the Art 2005-2007

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Organic Synthesis State of the Art 2005-2007

Douglass F. Taber University of Delaware

Newark, DE

WILEY A JOHN WILEY & SONS, INC., PUBLICATION

Copyright I 2008 by John Wiley & Sons, Inc All rights reserved

Published by John Wiley & Sons, Inc , Hoboken, New Jersey Published simultaneously in Canada

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Contents

Preface

1.

2.

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Synthesis of (-)- Littoralisone

Enantiocontrolled Construction of Oxygenated and Animated Stereogenic Centers

Catalytic Enantioselective Construction of Alkylated Stereogenic Centers

Catalytic Enantioselective Aldol/Mannich Reactions Leading to Extended Arrays of Stereogenic Centers

Alternative Strategies for the Construction of Extended Arrays of Stereogenic Centers

Synthesis of(-)- Avrainvillamide and (+)- Stephacidin B

Best Synthetic Methods: Oxidation

Best Synthetic Methods: Reduction

Selective Reactions of Alkenes

Synthesis of the Potent FBBP12 Ligand Antascomicin B

Best Synthetic Methods: Carbon-Carbon Bond Formation

Enantioselective Construction of Quaternary Centers

Pd-Mediated Arylation of Aromatic and Hetero Aromatic Rings

The Overman Route to Gelsemine

Stereoselective Construction of Oxygen Heterocycles

Enantioselective Construction of Naturally-Occurring Cyclic Ethers

Stereoselective Construction of Nitrogen Heterocycles

The Stork Synthesis of (-)- Reserpine

Stereocontrolled Construction of Azacyclic Natural Products

Preparation of Benzene Derivatives

Preparation of Heteroaromatics

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CONTENTS

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Preparation and Reactions of Carboxylic Acids, Esters and Amides

The Boger Route to (-)- Vindoline

Protection of C - 0 and C-N

New Catalysts and Strategies for Alkene Metathesis

Creative Applications of Alkene and Alkyne Metathesis in Total Synthesis: (+)-%epi-Xanthatin, (+)-Longicin, Latrunculin A, and Garsubellin A

Synthesis of Erythronolide A

Best Synthetic Methods: C-C Bond Formation

Catalytic Enantioselective Homologation of Aldehydes to Alcohols and Amines

Catalytic Enantioselective Construction of Alkylated Stereogenic Centers

Enantioselective Construction of Arrays of Stereogenic Centers

Adventures in Complex Indole Synthesis: (-)-Fixherindole I, (+)-Fischerindole G and (+)-Weltwitindolinone A

New Dienes and Dienophiles for Intermolecular and Intramolecular Diels-Alder Cycloaddtions

Organocatalytic Preparation of Enantiomerically-Pure Carbocycles

Carbocycle Construction by the Opening of Strained Rings: Synthesis of Tremulenolide A

The Corey Route to the Dolabellanes: Isoedunol and P-Araneosene

Transition-Metal Catalyzed Enantioselective Ring Construction

Best Synthetic Methods: Functional Group Transformation

Selective Reactions of Alkenes

Synthesis and Absolute Stereochemical Assignment of (-)-Galbulimima Alkaloid 13

Preparation of Benzene Derivatives

Preparation of Heteroaromatic Derivatives

Functional Group Transformation

Functional Group Protection

The Leighton Synthesis of Dolabelide D

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CONTENTS

46. Stereocontrolled Construction of N-Heterocycles

47. Stereocontrolled Construction of 0-Heterocycles

48. Stereocontrolled Synthesis of 0-Heterocyclic Natural Products

49. The Ready Synthesis of (-)-Nigellamine A,

50. Advances in the Diels-Alder Reaction: Synthesis of (+)-Lycoridine and of Dolabellatrienone

5 1. Enantioselective Carbocyclic Construction

52. Transition Metal Mediated Carbocyclic Construction

53. Synthesis of (-)-Colombiasin A and (-)-Elisapterosin B

54. Enantioselective Synthesis of C-N Ring Containing Natural Products

55. New Catalysts and Strategies for Alkene and Alkyne Metathesis

56. Heterocyclic Natural Products by Alkene Metathesis

57. Carbobyclic Natural Products by Alkene Metathesis

58. The Crimmins Synthesis of (+)-SCH 351448

59. Enantioselective Construction of Alcohols and Amines

6 1. Enantioselective Construction of Alkylated Stereogenic Centers

6 1. Enantioselective Construction of Arrays of Stereogenic Centers

62. The Sorensen Synthesis of (-)-Guanacastepene E

63. Selective Reactions of Alkenes

64. Best Synthetic Methods: C-C Bond Formation

65. Functional Group Protection and Deprotection

66. The Nicolaou Synthesis of Platensimycin

67. Stereocontrolled C - 0 Ring Construction

68. Stereocontrolled Natural Product Synthesis: Cyclic Ethers and Macrolides

69. Stereocontrolled C-N Ring Construction

70. Stereocontrolled Alkaloid Total Synthesis

71. The Fukuyama Synthesis of Morphine

73. Oxidation and Reduction in Organic Synthesis

73. Interconversion of Organic Functional Groups

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CONTENTS

74. Best Synthetic Methods: Carbon-Carbon Bond Formation

75. The Overman Synthesis of (-)-Sarah A

76. Recent Developments in Alkene Metathesis

77. Pushing the Limits of Alkene Metathesis in Natural Product Synthesis

78. Preparation of Benzene Derivatives

79. The Padwa Synthesis of Aspidophytidine

80. Synthesis of Heteroaromatics

8 1. Enantioselective Construction of Alcohols and Amines

82. Enantioselective Construction of Alkylated Stereogenic Centers

83. Enantioselective Construction of Arrays of Stereogenic Centers

84. The Gin Synthesis of Nominine

85. The Intramolecular Diels-Alder Reaction in Natural Product Synthesis

86. Catalytic Enantioselective Carbon-Carbon Ring Construction

87. New Directions in C-C Ring Construction: The Overman Synthesis of Guanacastepene N

88. The Pettus Synthesis of (+)-Rishirilide B

89. Selective Reactions of Alkenes

90. Selective C-H Functionalization

91. New Methods for Carbon-Carbon Bond Formation

92. The Nakada Synthesis of (+)-Digitoxigenin

93. Preparation of Benzene Derivatives

94. Preparation of Heteroaromatics: The Movassaghi Synthesis of (+)-Chimonanthine

95. Organic Functional Group Transformation

96. Organic Functional Group Protection

97. The Trost Synthesis of (-)-Terpestacin

98. Stereoselective C-N Ring Construction

99. Stereoselective C - 0 Ring Construction

100. Synthesis of (-)-Blepharocalyxin D, (-)-Lasonolide A, and Attenol A

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CONTENTS

101. The Dark Synthesis of Vigulariol 20 1

102. Enantioselective Organocatalytic Synthesis of Carbocycles: The 203

103. Transition-metal Mediated Synthesis of Carbocycles: The Snapper 205

Iwabuchi Synthesis of (+)-Juvabione

Synthesis of Pleocarpenone

Synthesis of (+)-Fusicoauritone 104. Enantioselective Construction of Carbocycles: The Williams 207

105. C-H Functionalization: The White Reagent 207

Author Index 209

Reaction Index 219

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Preface

Several years ago, I was approached about updating Rich Larock’s valuable com- pendium of organic transformations. As I contempated that task, it became clear to me that what the organic synthesis community needed more was a real-time overview of current developments. With the able assistance of Reto Mueller, web- master of www.organic-chemistry.org, I started writing weekly Organic Highlights columns. These soon developed into mini-reviews of areas of current interest in or- ganic synthesis. The Highlights columns provide in-depth coverage of new devel- opments across the field. Some topics, such as asymmetric organocatalysis and C-H functionalization, are often mentioned in the scientific press. Other topics, such as new methods for C-C bond construction, receive little popular notice, but are at least as important.

There was still the problem of information retrieval. To this end, Wiley was per- suaded to publish the first two years of the Highlights columns in book form, Or- ganic Synthesis: State of the Art 2003-2005, with author and transformation indices. This volume continues that series, with cumulative indices. With both volumes in hand, one can at a glance be up to date on a particular topic. For many recent ad- vances, including organocatalysis, this level of search provides a comprehensive overview of the field. To make in-depth review more convenient, each of the week- ly columns is still up on the web, with links to the original journal articles.

I often consult these volumes myself in my day-to-day work of teaching and re- search. These two volumes together (and the later biennial volumes that will fol- low) are a valuable resource that should be on the bookshelf of every practicing or- ganic synthesis chemist.

DOUGLASS F. TABER Newark, DE March 1, 2008

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Synthesis of (-)-Littoralisone January 2,2006

The loss of mental function associated with aging is thought to be due at least in part to the degradation of netirite connections between neurons. Natural products such as (-)-littoralisone 3 that promote neurite outgrowth in cell culture are therefore interesting lead compounds for pharmaceutical discovery. The synthesis of 3 recently reported (J . Am. Chem. SOC. 2005,127, 3696) by David W. C. MacMillan of Caltech uses organocatalysis to assemble 1, to control the relative configuration of the ring system of 2, and to assemble the glucose component of 3.

OH

1 2 3

The preparation of 1 began with conmercial enantiomerically-pure citronellol4. Ozonolysis of the ester delivered the aldehyde 5, which was hydroxylated with high diastereocontrol (enantiocontrol), using the proline-catalyzed procedure developed by MacMillan (LINK. Organic Highlights 26 January 2004). Protection and homologation o f 6 then gave 1.

0

- & EH0”f& D-proline - R 3 S i 0 , , , c H 0 OH OC(0)R OC(0)R

4 5 6 1

L-proline POCI,

DMF OAc

2 7 0

1