Organic Chemistry in Action (eBook)

The Design of Organic Synthesis

F. Serratosa (Autor)

eBook Download: PDF

2013 | 1. Auflage
418 Seiten
Elsevier Science (Verlag)
978-1-4832-9092-8 (ISBN)

Infos

Contrary to all other books in the field of organic synthesis, this volume combines Corey's methodology, which is based on the concept of synthon and retrosynthetic analysis, with Evans' methodology based on the `Lapworth model' of alternating polarities. Using this approach, the formation of carbon-carbon bonds and the manipulation of functional groups are treated together, whereas the stereochemical aspects are considered separately. Emphasis is laid on the importance of rigid structures, whether in the starting materials, the synthetic intermediates or the transition states, as a means of controlling the stereochemistry of the organic compounds.

Enclosed with the book is a copy of a miniprogram (CHAOS) for an IBM PC, or fully compatible computers, which is an interactive program, affording the beginner a fast and easy way of learning, exploring and looking for new synthetic schemes of molecules of moderate complexity. As a textbook on organic synthesis, this volume will be of immense value at university level.

Inhalt

Front Cover 1
Organic Chemistry in Action: The Design of Organic Synthesis 4
Copyright Page 5
Table of Contents 14
Studies in Organic Chemistry 6
Dedication 8
PREFACE 10
ACKNOWLEDGEMENTS 12
Chapter 1. HEURISTICS AND ORGANIC SYNTHESIS. PURE SUBSTANCES 24
1.1. Organic synthesis as a heuristic activity 24
1.2. Pure substances. Language: The Classical Structural Theory 25
1.3. The objectives of organic synthesis 28
1.4. Synthesis as a sequence of unequivocal steps. Economy: conversion, selectivity and yield. Starting materials 32
1.5. Carbon skeleton, functional group manipulation and stereochemical control. Rule of maximum simplicity 37
1.6. Molecular complexity and synthetic analysis 42
REFERENCES 45
Chapter 2. THE REACTIVITY OF ORGANIC MOLECULES 47
2.1. Some general remarks on the reactivity of organic compounds 47
2.2. Molecules as ionic aggregates. The Lapworth-Evans model 49
2.3. Classification of functional groups according to D.A. Evans 52
2.4. Consonant and dissonant bifunctional relationships 59
REFERENCES 65
Chapter 3. METHODOLOGIES 66
3.1.The retrosynthetic process. Methodologies for the design of organic synthesis. The synthesis tree 66
3.2. Auxiliary physical techniques in the synthesis of organic compounds 72
3.3. Structural synthetic analysis, simplification and generation of the intermediate precursors of the "synthesis tree". Principle of microscopic reversibility 75
REFERENCES 83
Chapter 4. SYNTHETIC STRUCTURAL ANALYSIS. SIMPLIFICATION. HETEROLYTIC DISCONNECTIONS: HEURISTIC PRINCIPLES 85
4.1. Symmetry 85
4.2. Functional groups 91
4.3. The carbon skeleton: chains, rings and appendages 103
REFERENCES 109
Chapter 5. SYNTHESIS OF DISSONANT SYSTEMS 111
5.1. Illogical disconnections: reactivity inversion 111
5.2. Plausible disconnections: dissonant three-membered rings 124
5.3. Sigmatropic rearrangements 138
5.4. Reconnection of bifunctional dissonant relationships to rings 143
5.5. Homolytic disconnections: couplings involving electron-transfer 144
REFERENCES 155
Chapter 6. CYCLIC AND POLYCYCLIC SYSTEMS 158
6.1. RETRO-ANNULATIONS 160
6.2. CYCLOREVERSIONS 168
6.3. HETEROCYCLIC COMPOUNDS 174
REFERENCES 180
Chapter 7. SYSTEMS WITH UNUSUAL STRUCTURAL FEATURES: QUATERNARY CARBON ATOMS, MEDIUM-SIZED RINGS AND BRIDGED SYSTEMS 183
7.1. REARRANGEMENTS AND INTERNAL FRAGMENTATIONS 183
7.2. BRIDGED SYSTEMS 191
REFERENCES 206
Chapter 8. STEREOCHEMICAL CONTROL IN CYCLIC AND POLYCYCLIC SYSTEMS 208
8.1. INTRODUCTION 208
8.2. SPECIFICITY, SELECTIVITY, ORDER AND NEGATIVE ENTROPY 211
8.3. DIASTEREOSELECTIVITY IN CYCLIC AND POLYCYCLIC SYSTEMS 213
REFERENCES 222
Chapter 9. ACYCLIC DIASTEREOSELECTION 224
9.1. TEMPORARY BRIDGES AND AUXILIARY RINGS AS CONTROL ELEMENTS IN ACYCLIC DIASTEREOSELECTION 224
9.2. DIASTEREOSELECTIVE CONTROL THROUGH HIGHLY ORDERED TRANSITION STATES 227
9.3. ENANTIOSELECTIVE CONTROL 236
9.4. ASYMMETRIC EPOXIDATION AND DIHYDROXYLATION 260
REFERENCES 265
Chapter 10. ORGANIC SYNTHESIS. CONCLUDING REMARKS 269
10.1. Biogenetic considerations 269
10.2. Control elements 271
10.3. Logic-centred synthetic analysis methodology: Summary 283
10.4. General strategies 286
REFERENCES 287
Chapter 11. COMPUTER-ASSISTED ORGANIC SYNTHESIS 290
11.1. Computers, computation, computerisation and artificial intelligence. The "exploration tree" 290
11.2. Computer-assisted organic synthesis 292
11.3. CHAOS, a heuristic aid for designing organic synthesis 294
REFERENCES 303
Chapter 12. SELECTED ORGANIC SYNTHESES 305
12.1. TWISTANE 306
REFERENCES 320
12.2. LUCIDULINE 321
REFERENCES 336
12.3. CARYOPHYLLENES 338
REFERENCES 348
12.4. STEREOCONTROLLED SYNTHESIS OF 1, 3, 5...(2n +1) POLYOLS. SYNTHESIS AND STEREOCHEMICAL ASSIGNMENT OF THE C(1)-C(10) FRAGMENT OF NYSTATIN A1 348
REFERENCES 352
Appendix 1: GRAPH THEORY. MOLECULAR COMPLEXITY INDICES 354
REFERENCES 361
Appendix 2: CHAOS: INSTRUCTION MANUAL 362
Appendix 3: CHAOS: DISCONNECTION GROUPS 397
Appendix 4: SUGGESTED EXERCISES TO BE SOLVED BY CHAOS 408
SUBJECT INDEX 410

Produkt-Details

• Erscheint lt. Verlag: 22.10.2013
• Sprache: englisch
• Themenwelt: Naturwissenschaften ► Chemie ► Anorganische Chemie
• Themenwelt: Naturwissenschaften ► Chemie ► Organische Chemie
• Themenwelt: Naturwissenschaften ► Chemie ► Physikalische Chemie
• Themenwelt: Naturwissenschaften ► Physik / Astronomie ► Atom- / Kern- / Molekularphysik
• Themenwelt: Technik
• ISBN-10: 1-4832-9092-1 / 1483290921
• ISBN-13: 978-1-4832-9092-8 / 9781483290928