Rubiralta / Giralt / Diez Piperidine

Structure, Preparation, Reactivity, and Synthetic Applications of Piperidine and its Derivatives
1. Auflage 2013
ISBN: 978-1-4832-9093-5
Verlag: Elsevier Science & Techn.
Format: PDF
Kopierschutz: 1 - PDF Watermark

E-Book, Englisch, Band Volume 43, 460 Seiten, Web PDF

Reihe: Studies in Organic Chemistry

Piperidine, one of the simplest heterocyclic systems, is found in nature as part of several alkaloid compounds. Both natural and especially unnatural piperidine derivatives present interesting pharmacological properties. From a structural viewpoint, the conformation of piperidine has been the subject of one of the fiercest controversies in structural organic chemistry in the last few years. As a result of the combined use of several spectroscopic techniques, the conformational behavior of most types of piperidine-related compounds has been clarified. Some piperidine derivatives, namely, N-acylpiperidine, &agr;-cyanopiperidines and piperidones are extremely useful and versatile intermediates in organic synthesis. The present book offers an updated and integrated view of all these topics. The aim of the book is twofold. Firstly, to reveal to the reader the combined use of different spectroscopic data, to facilitate an insight into the structure and conformational properties of any new piperidine derivative. Secondly, to establish a consistent link between conformation and reactivity for a variety of piperidine derivatives. Such a bridge is a key step for stereocontrol when dealing with the application of piperidine derivatives as synthetic intermediates. The book is conceived so that most of the information comes from visual inspection of the very abundant graphic material. An exhaustive subject index of more than 450 entries is also included.

Autoren/Hrsg.

Rubiralta, M.

Giralt, E.

Diez, A.

Inhaltsverzeichnis

1;Front Cover;1
2;Piperidine: Structure, Preparation, Reactivity, and Synthetic Applications of Piperidine and its Derivatives;4
3;Copyright Page;5
4;Table of Contents;10
5;Preface;8
6;Chapter 1. PIPERIDINE. A GENERAL SURVEY;18
6.1;1.1. SYNTHETIC ASPECTS;20
6.2;1.2. PIPERIDINE AS A SOLVENT;27
6.3;1.3. PIPERIDINE AS A BASE AND AS A NUCLEOPHILE;27
6.4;1.4. REACTIVITY OF PIPERIDINE. A PREVIEW;31
6.5;1.5. REFERENCES;37
7;Chapter 2. CONFORMATIONAL ANALYSIS OF PIPERIDINE;41
7.1;2.1. THE CHEMICAL SHIFT DIFFERENCE (dae) METHOD;43
7.2;2.2. CONTROVERSY AND THE PRESENT SITUATION;45
7.3;2.3. REFERENCES AND NOTES;49
8;Chapter 3.1H NMR PROPERTIES OF PIPERIDINE DERIVATIVES;51
8.1;3.1. INTRODUCTION;52
8.2;3.2.1H NMR OF PIPERIDINE AND METHYLPIPERIDINES;52
8.3;3.3. 2-ARYL-4-PIPERIDONES;77
8.4;3.4. ARYLPIPERIDINES;80
8.5;3.5. APPLICATION OF TWO-DIMENSIONAL NMR TECHNIQUES TO PIPERIDINE DERIVATIVES;86
8.6;3.6. REFERENCES;101
9;Chapter 4.13C NMR SPECTROSCOPY OF PIPERIDINE DERIVATIVES;105
9.1;4.1. NITROGEN INVERSION IN PIPERIDINE AND N-METHYL PI PERI DINE;106
9.2;4.2. C-ALKYLPIPERIDINES;107
9.3;4.3. N-INVERSION IN HINDERED PIPERIDINES;110
9.4;4.4. METHYL SUBSTITUTED PIPERIDINIUM SALTS;111
9.5;4.5. CONFORMATIONAL EQUILIBRIA IN QUATERNARY PIPERIDINIUM SALTS;114
9.6;4.6. 4-PHENYLPIPERIDINES AND 4-PHENYL-4-PIPERIDINOLS;116
9.7;4.7. 3-ARYLPI PERI DINES;126
9.8;4.8. PIPERIDONES AND 2-ARYL-4-PIPERIDONES;128
9.9;4.9. PIPERIDINES WITH FUSED RINGS;133
9.10;4.10. AZABICYCLO[3.3.1]NONANE DERIVATIVES;141
9.11;4.11. REFERENCES;148
10;Chapter 5. MASS SPECTROMETRY OF PIPERIDINE DERIVATIVES;152
10.1;5.1. SIMPLE PIPERIDINE COMPOUNDS:PIPERIDINE N-METHYLPIPERIDINE AND PIPERIDINE ALKALOIDS;153
10.2;5.2. PIPERIDONES AND 4,4-ETHYLENEDIOXYPIPERIDINES;163
10.3;5.3. PIPERIDINOLS AND 4-AMINOPIPERIDINES;170
10.4;5.4. N-ACYLPIPERIDINES;174
10.5;5.5. PIPERIDINE N-OXIDES;175
10.6;5.6. BICYCLIC PIPERIDINE COMPOUNDS;176
10.7;5.7. STRUCTURAL ELUCIDATION OF ALKALOIDS;185
10.8;5.8. REFERENCES;186
11;Chapter 6. 2-ARYLPIPERIDINES AS SUITABLE MODELS FOR STUDYING ROTATIONAL BARRIERS AROUND Csp2- Csp3 BONDS;189
11.1;6.1. INTRODUCTION;190
11.2;6.2. 3-ARYLPIPERIDINOLS: DENDROCREPINE ALKALOID;190
11.3;6.3. 2-ARYL-4-PIPERIDONES;191
11.4;6.4. REFERENCES;209
12;Chapter 7. N-ACYLPIPERIDINES. A USEFUL TOOL FOR STEREOCONTROL IN ORGANIC SYNTHESIS;210
12.1;7.1. STUDY OF ROTATIONAL EQUILIBRIUM AROUND THE AMIDE BOND IN N-ACYLPIPERIDINES BY1H NMR SPECTROMETRY;211
12.2;7.2. STRUCTURAL ELUCIDATION OF N-ACYLPIPERIDINES BY 13C NMR DETERMINATION OF AMIDE ROTATIONAL BARRIERS;227
12.3;7.3. N-ACYLPIPERIDINES AS A USEFUL TOOL FOR STEREOCONTROL IN ORGANIC SYNTHESIS;236
12.4;7.4. REFERENCES;240
13;Chapter 8. STRUCTURE AND SYNTHETIC APPLICATIONS OF a-CYANOTETRAHYDROPYRIDINES AND a-CYANOPIPERIDINES;242
13.1;8.1. SYNTHESIS AND SYNTHETIC APPLICATIONS OF 2-CYANO-1,2,3,6-TETRAHYDROPYRIDINES;243
13.2;8.2. SYNTHESIS AND SYNTHETIC APPLICATIONS OF 2-CYANO-1,2,5,6-TETRAHYDROPYRIDINES;252
13.3;8.3. SYNTHESIS AND SYNTHETIC APPLICATIONS OF 2-CYANOPIPERIDINES;264
13.4;8.4. SYNTHESIS AND SYNTHETIC APPLICATIONS OF 2-CYANO-6-OXAZOLOPIPERIDINES;289
13.5;8.5. EXOCYCLIC a-CYANOPIPERIDINES;299
13.6;8.6. STEREOCHEMICAL ASPECTS OF 2-CYANOPIPERIDINES AND 2-CYANOTETRAHYDROPYRIDINES;307
13.7;8.7. Í MR SPECTROSCOPY OF 2-CYANOPIPERIDINES AND 2-CYANOTETRAHYDROPYRIDINES;314
13.8;8.8. REFERENCES;325
14;Chapter 9. PIPERIDONES AS USEFUL INTERMEDIATES IN ORGANIC SYNTHESIS;330
14.1;9.1. SYNTHESIS OF PIPERIDONES;331
14.2;9.2. SYNTHESIS OF ARYLPIPERIDONES;370
14.3;9.3. SYNTHETIC APPLICATIONS OF PIPERIDONES;390
14.4;9.4. REFERENCES;438
15;10. SUBJECT INDEX;452