Paulmier / Perlmutter Selenium Reagents & Intermediates in Organic Synthesis

1. Auflage 2013
ISBN: 978-1-4832-8640-2
Verlag: Elsevier Science & Techn.
Format: PDF
Kopierschutz: 1 - PDF Watermark

E-Book, Englisch, Band Volume 4, 478 Seiten, Web PDF

Reihe: Tetrahedron Organic Chemistry

The explosive growth of organoselenium chemistry over the past 12 years can be attributed to the specific properties of organic selenium molecules, which fit the requirements of modern organic synthesis. Most of them are well adapted to chemo-, regio- and stereo-selectivities. In addition, they can be used in mild experimental conditions which are compatible with the stability of both substrates and products in the preparation of unsaturated and functional complex molecules, especially in the field of natural products. This book describes and illustrates different synthetic routes to organic structures using selenium reagents or intermediates. The approach emphasizes that such transformations are simple, efficient and often carried out at room temperature. The scope ranges from the preparation of both inorganic and organic selenium reagents, through descriptions of structure, toxicity, biological aspects and nuclear magnetic resonance, to applications of specific selenium compounds in various syntheses including natural products and biologically active compounds.

Autoren/Hrsg.

Paulmier, C.

Perlmutter, Patrick

Inhaltsverzeichnis

1;Front Cover;1
2;Selenium Reagents and Intermediates in Organic Synthesis;4
3;Copyright Page;5
4;Table of Contents;10
5;Dedication;6
6;FOREWORD;8
7;ACKNOWLEDGMENTS;9
8;INTRODUCTION;16
9;CHAPTER I.
GENERAL ASPECTS OF SELENOORGANIC CHEMISTRY;19
9.1;1- Functional groups and structures;19
9.2;2- Biological aspects;22
9.3;3- Commercially available products;22
9.4;4- Synthesis and properties of inorganic selenium reagents;23
9.5;5- Nuclear magnetic resonance analysis;32
9.6;References;36
10;CHAPTER II.
SELENOORGANIC FUNCTIONAL GROUPS;40
10.1;1- Selenols;40
10.2;2- Selenocyanates;42
10.3;3- Diselenides;47
10.4;4- Alkane-, areneselenolate anions and analogous reagents;51
10.5;5- Selenenyl halides;53
10.6;6- Selenenic acids and derivatives;55
10.7;7- Seleninic acids and derivatives;59
10.8;8- Selenonic acids;63
10.9;9- Selenious acid derivatives;64
10.10;10- Selenic acid esters;65
10.11;References;66
11;CHAPTER III.
SELENOCARBONYL AND SELENOCARBOXYLIC FUNCTIONAL GROUPS;73
11.1;1- Selenoaldehydes;73
11.2;2- Selenoketones or selones;75
11.3;3- Selenoketenes;78
11.4;4- Selenolesters;78
11.5;5- Isoselenocyanates and selenoureas;85
11.6;6- Selenonesters;88
11.7;7- Selenoamides;92
11.8;8- Selenoimidates;94
11.9;References;95
12;CHAPTER IV.
SYNTHESIS AND PROPERTIES OF SELENIDES;99
12.1;1- Selenide synthesis;99
12.2;2- Selenide properties;117
12.3;3- Synthesis of selenoacetals and triselenoorthoalkanoates;125
12.4;4- Properties of selenoacetals and triselenoorthoalkanoates;129
12.5;References;131
13;CHAPTER V.
SELENOXIDES AND SELENONES;139
13.1;1- Formation of selenoxides;140
13.2;2- General properties of selenoxides;143
13.3;3- Syn-elimination reaction;147
13.4;4- Applications of the syn-elimination reaction;153
13.5;5- [2,3J-Sigmatropic rearrangement of allylic selenoxides;158
13.6;6- Synthetic applications of the [2,3J-sigmatropic rearrangement;165
13.7;7- N-Substituted selenilimines;165
13.8;8- Selenones;168
13.9;References;172
14;CHAPTER VI.
SELENONIUM SALTS AND SELENONIUM YLIDES;177
14.1;1- Preparation of selenonium salts;177
14.2;2- Properties of selenonium salts;180
14.3;3- Preparation of selenonium ylides;184
14.4;4- Properties of selenonium ylides;188
14.5;References;194
15;CHAPTER VII.
ADDITION REACTIONS;197
15.1;1- Selenol additions to activated double and triple bonds;197
15.2;2- Addition of areneselenenyl halides to olefins;200
15.3;3- Addition reactions to olefins with nucleophiles other than halides;204
15.4;4- Addition reactions to enols, enol ethers, enamines;213
15.5;5- Addition reactions to allylic alcohols and derivatives;220
15.6;6- Addition reactions to conjugated systems;223
15.7;7- Addition reactions to acetylenic and allenic compounds;225
15.8;8- Free-radical additions to double and triple bonds;229
15.9;9- Other addition reactions;233
15.10;References;236
16;CHAPTER VIII.
ADDITION REACTIONS WITH CYCLIZATION;243
16.1;1- Cyclofunctionalization of unsaturated alcohols;244
16.2;2- Cyclofunctionalization of unsaturated carboxylic acids;247
16.3;3- Cyclofunctionalization of unsaturated amines and derivatives;253
16.4;4- Cyclofunctionalization of unsaturated thiols and thioacetates;255
16.5;5- Cyclofunctionalization of allenic phosphonates and phosphinates;256
16.6;6- Cyclofunctionalization of 1,5- and 1,6-dienes;257
16.7;7- Cyclofunctionalization of enals and enones;259
16.8;8- Cyclization with carbon-carbon bond formation;261
16.9;References;267
17;CHAPTER IX.
SELENIUM-STABILIZED CARBANIONS;271
17.1;1- General considerations on stabilized carbanions;272
17.2;2- Formation of selenium-stabilized carbanions;275
17.3;3- Reactions of selenium-stabilized carbanions with electrophiles;279
17.4;4- Reactivity of the allylic carbanions;288
17.5;5- Reactivity of the seleninyl and selenonyl carbanions;290
17.6;6- Reactions with conjugated enals and enones;293
17.7;References;297
18;CHAPTER X.
UNSATURATED SELENIDES, SELENOXIDES AND SELENONES;300
18.1;1- Preparation of vinylic and acetylenic selenides;300
18.2;2- Properties of vinylic and acetylenic selenides;307
18.3;3- Specific properties of vinylic selenoxides and selenones;314
18.4;4- Preparation of allylic selenides;319
18.5;5- Properties of allylic, propargylic and dienic selenides;322
18.6;References;329
19;CHAPTER XI.
HYDROXY- AND CARBONYL-SELENIUM STRUCTURES;334
19.1;1- Synthesis of ß-hydroxyselenides;334
19.2;2- Properties of ß-hydroxyselenides;337
19.3;3- Properties of .- and d-hydroxyselenides;348
19.4;4- Synthesis of a-selenocarbonyl compounds;349
19.5;5- Properties of a-selenocarbonyl compounds;354
19.6;6- Synthesis and reactions of conjugated a-selenocarbonyl compounds;360
19.7;References;365
20;CHAPTER XII.
OXIDATION REACTIONS;368
20.1;1- Oxidation with selenium dioxide;368
20.2;2- Oxidation with benzeneseleninic anhydride;379
20.3;3- Oxidation with areneseleninic acids;386
20.4;4- Oxidation with selenoxides and selenuranes;391
20.5;5- Allylic chlorination and amination;395
20.6;References;397
21;CHAPTER XIII. REDUCTION REACTIONS AND OTHER USES OF SELENIUM REAGENTS;402
21.1;1- Reduction reactions;402
21.2;2- Synthetic uses of carbon oxide selenide;407
21.3;3- Synthetic uses of elemental selenium;410
21.4;4- Synthetic uses of selenols and alkali selenolates;411
21.5;5- Alkylation and acylation reactions;414
21.6;References;414
22;CHAPTER XIV. SPECIAL STRUCTURES AND NATURAL PRODUCTS AND BIOLOGICALLY ACTIVE COMPOUNDS;417
22.1;1- Synthesis of silicon compounds;418
22.2;2- Synthesis of particular unsaturated structures;422
22.3;3- Synthesis of unsaturated and functional aliphatic structures;424
22.4;4- Synthesis of unsaturated and functional cyclic structures;427
22.5;5- Synthesis of unsaturated and functional cyclic ethers;434
22.6;6- Synthesis of unsaturated lactones;437
22.7;7- Synthesis of unsaturated and functional nitrogen heterocyclic compounds;443
22.8;References;448
23;AUTHOR INDEX;452
24;SUBJECT INDEX;470