Lindberg Strategies and Tactics in Organic Synthesis

1. Auflage 2013
ISBN: 978-0-08-092429-8
Verlag: Elsevier Science & Techn.
Format: PDF
Kopierschutz: 1 - PDF Watermark

E-Book, Englisch, Band Volume 2, 469 Seiten, Web PDF

Reihe: Strategies and Tactics in Organic Synthesis

This is a unique account of the synthesis of organic molecules. All of the contributors are acknowledged experts in organic synthesis.

Autoren/Hrsg.

Lindberg, Thomas

Inhaltsverzeichnis

1;Front Cover;1
2;Strategies and Tactics in Organic Synthesis;4
3;Copyright Page;5
4;Table of Contents;6
5;CONTRIBUTORS;12
6;FOREWORD;14
7;PREFACE;16
8;Chapter 1. DIELS-ALDER REACTIONS OF HETEROCYCLIC AZADIENES: DEVELOPMENT OF A STRATEGY FOR THE TOTAL SYNTHESIS OF STREPTONIGRIN, LAVENDAMYCIN, AND SYNTHETIC QUINOLINE-5,8-QUINONES;18
8.1;I. Introduction;19
8.2;II. Methodology Development. Inverse Electron Demand Diels-Alder
Reactions of Electron-Deficient Azadienes: 1,2,4-Triazines,
1,3,5-Triazines, 1,2,4,5-Tetrazines, 1,2-Diazines;23
8.3;III. Formal Total Synthesis of Streptonigrin;25
8.4;IV. Total Synthesis of Lavendamycin Methyl Ester;39
8.5;V. Divergent Introduction of the Streptonigrin/Lavendamycin Quinoline-5,8-quinone AB Ring Systems;55
8.6;VI. Structure-Activity Studies: Experimental Probes of the Chemical
Mechanism of Action of Streptonigrin, Lavendamycin, and
Synthetic Quinoline-5,8-quinones;58
8.7;Acknowledgments;68
8.8;References;68
9;Chapter 2. STUDIES IN SESQUITERPENE SYNTHESIS: (±)-QUADRONE AND (+)-PHYLLANTHOCIN;74
9.1;I. Introduction;74
9.2;II. Quadrone;77
9.3;III. Phyllanthocin;88
9.4;IV. Summary;101
9.5;Acknowledgments;103
9.6;References;103
10;Chapter 3. THE TOTAL SYNTHESIS OF RETIGERANIC ACID;108
10.1;I. Introduction;108
10.2;II. Retrosynthetic Analysis: The Initial Plan;109
10.3;III. The frans-Hydrindane Problem: Rapid Progress and False Hope;111
10.4;IV. The Diels-Alder Reaction: Revealing an Error;113
10.5;V. The frans-Hydrindane Problem: Multiple Solutions;115
10.6;VI. Success of the Diels-Alder Reaction: Construction of a Tricyclic Intermediate;122
10.7;VII. Reversible 2 + 2s: A Change in Strategy;123
10.8;VIII. Success of the Intramolecular 2 + 2: Construction of a Pentacyclic Intermediate;129
10.9;IX. Ring Expansions and Contractions: The Total Synthesis of Retigeranic Acid;131
10.10;X. The Natural Product: Retigeranic Acid-A and Retigeranic Acid-B;134
10.11;Acknowledgments;136
10.12;References;136
11;Chapter 4.
CARBOCYCLES FROM
CARBOHYDRATES:
THE "ANNULATED
SUGAR" APPROACH;140
11.1;I. Introduction;140
11.2;II. The General Protocol;141
11.3;III. Synthetic Design;144
11.4;IV. Actinobolin;144
11.5;V. The Oxahydrindene Moiety of Avermectins;154
11.6;VI. The Trichothecane System;159
11.7;VII. The Triquinane System;170
11.8;VIII. Conclusions;175
11.9;Acknowledgments;176
11.10;References;176
12;Chapter 5. d-VALEROLACTONE ANNULATION: APPLICATION TO THE TOTAL SYNTHESIS OF QUADRONE;180
12.1;I. Introduction;180
12.2;II. Background;181
12.3;III. Methods for d-Valerolactones and a-Pyrones;183
12.4;IV. Basic Strategy for Quadrone;190
12.5;V. Synthesis of Quadrone;191
12.6;VI. Conclusion;203
12.7;Acknowledgments;203
12.8;References;203
13;Chapter 6. THE TOTAL SYNTHESIS OF SAXITOXIN;208
13.1;I. Introduction;208
13.2;II. The Nitrile Oxide Route to Saxitoxin;211
13.3;III. The Azomethine Imine Route to Saxitoxin;216
13.4;IV. Summary;234
13.5;Acknowledgements;235
13.6;References;235
14;Chapter 7. PROBLEM SOLVING IN ORGANIC SYNTHESIS: THE
FALSE STEPS, FAILED PATHWAYS, AND ULTIMATELY
SUCCESSFUL ROUTE TO THE BOTTOM HALF OF
IVERMECTIN;238
14.1;I. Introduction;238
14.2;II. The Problem;239
14.3;III. Intramolecular N-Furfurylacrylamide Diels-Alder Approach;243
14.4;IV. Background for Choosing Alternative Approach;254
14.5;V. Furan—Coumalate Diels-Alder Approach;261
14.6;VI. Conclusion;275
14.7;Acknowledgments;276
14.8;References;277
15;Chapter 8. SYNTHESIS OF THE INDOLE ALKALOID a-CYCLOPIAZONIC ACID (aCA) BY TWO SULFUR-MEDIATED REACTIONS: DISCOVERY OF A USEFUL DIORGANOZINC REACTION;280
15.1;I. Introduction;280
15.2;II. Synthesis of aGA;285
15.3;III. Application of the Zinc Reaction to Phenylthio Glycosides: A New C-Glycoside Synthesis;301
15.4;IV. Conclusions;305
15.5;Acknowledgments;305
15.6;References;306
16;Chapter 9. A UNIFIED STRATEGY FOR THE SYNTHESIS OF ALKALOIDS OF THE YOHIMBOID, HETEROYOHIMBOID, AND CORYNANTHEIOID FAMILIES;308
16.1;I. Introduction;308
16.2;II. Formulation of the Strategy;310
16.3;III. Preliminary Model Studies;313
16.4;IV. The First-Generation Approach;315
16.5;V. The Second-Generation Approach;329
16.6;VI. Conclusions and Future Directions;336
16.7;Acknowledgments;337
16.8;References;337
17;Chapter 10.
EVOLUTION OF A STRATEGY FOR THE
SYNTHESIS OF OLIVOMYCIN A:
DEVELOPMENT OF METHODOLOGY
FOR THE DIASTEREO- AND
ENANTIOSELECTIVE SYNTHESIS OF
CARBOHYDRATES FROM ACYCLIC
PRECURSORS;340
17.1;I. Introduction;340
17.2;II. A Highly Stereoselective Total Synthesis of the Natural Enantiomer of Olivin;342
17.3;III. Progress Toward the Synthesis of Olivomycin A;363
17.4;IV. Concluding Remarks;379
17.5;Acknowledgments;379
17.6;References;380
18;Chapter 11. EVOLUTION OF A SYNTHETIC STRATEGY, PART II: TOTAL SYNTHESIS OF (-)-CASBENE AND (-)-BERTYADIONOL;386
18.1;I. Introduction;387
18.2;II. General Background: A Continuing Fascination with the Diterpenes;388
18.3;III. Development of a Unified Approach to Casbene and the Lathyrane Diterpenes: The Cornerstone of This Synthetic Venture;392
18.4;IV. Casbene: The Initial Target;394
18.5;V. Total Synthesis of ( — )-Bertyadionol: A More Challenging Target;402
18.6;VI. Summary;428
18.7;Acknowledgments;428
18.8;References;428
19;Chapter 12. A New Strategy for the Synthesis of Polyquinanes;432
19.1;I. Introduction;432
19.2;II. Furan Diels-Alder Reactions;433
19.3;III. Extension to the Synthesis of Fused Five-Membered Carbocyclic Rings;435
19.4;IV. Approach to the Synthesis of Quadrone;437
19.5;V. Triquinane Strategy;442
19.6;VI. Synthesis of Silphinene, and Angularly Fused Triquinane;444
19.7;VII. Synthesis of .9(12)-Capnellene; a Linearly Fused Triquinane;448
19.8;VIII. Conclusion;453
19.9;Acknowledgments;454
19.10;References;454
20;Chapter 13. EXPLORATIONS TOWARD PSEUDOMONIC ACID C;456
20.1;I. Introduction;456
20.2;II. General Strategy and Objectives;458
20.3;III. Difficult Beginnings: Stereocontrol in Tetrahydropyrans;460
20.4;IV. Phase Two: Stereoselective Synthesis of the Tetrahydropyran Component;468
20.5;V. The Final Stages: It's Never Over Until It's Over;474
20.6;VI. Conclusion;479
20.7;Acknowledgments;479
20.8;References;480
21;GLOSSARY OF ABBREVIATIONS;482
22;INDEX;484