Organoselenium Chemistry I: Functional Group Transformations

231 Pages·1988·6.4 MB·English

by  Professor Dr. Alain Krief, Professor Dr. László Hevesi (auth.)

Alain Krief· Laszlo Hevesi
Organoselenium
Chemistry I
Functional Group Transformations
With 262 Schemes
Springer-Verlag
Berlin Heidelberg New York
London Paris Tokyo
Professor Dr. Alain Krief
Professor Dr. Laszl6 Hevesi
Facultes Universitaires Notre-Dame de la Paix
Departement de Chimie
B - 5000 Namur (Belgium)
ISBN-13: 978-3-642-73243-0 e-ISBN-13: 978-3-642-73241-6
DOl: 10.1007/978-3-642-73241-6
Library of Congress Cataloging-in-Publication Data
Krief, A. (Alain), 1942 - Organoselenium chemistry I. Bibliography: p. 1. Organoselenium com-
pounds. I. Hevesi, L. (UiszI6), 1941 -. II. Title.
QD412.S5K75 1988 547'.05724 87-36926
ISBN-13: 978-3-642-73243-0
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© by Springer-Verlag Berlin Heidelberg 1988
Softcover reprint of the hardcover 1st edition 1988
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215213020-543210
Foreword
During the last fifteen years organoselenium chemistry underwent a spectacular
mutation: from an exotic area of science practised by a few specialists it became a
relatively well mastered and widely used methodology by synthetic organic
chemists. The key to this success is that a fair number of selenium based reagents
and reactions have been discovered, which are able to perform specific transfor-
mations selectively and often under very mild conditions. The most popular of
these are:
i) oxidation of various types of substrates by selenium dioxide,
ii) oxidations using benzeneseleninic anhydride,
iii) selenoxide syn elimination leading to olefins,
iv) [2,3] sigmatropic rearrangement of allylic selenoxides and selenimides giving
rise to allyl alcohols and allylic amines respectively,
v) electrophilic selenium-induced ring closures leading to lactones, to carbo-
and heterocycles followed by reductive or oxidative deselenylation,
vi) carbon-carbon bond forming reactions using selenium-stabilized organo-
metallics or carbocationic species,
vii) radical cyclisation triggered by homolytic C-Se bond cleavage.
Although organoselenium compounds have been known for more than a century,
it is only since the discovery of selenium dioxide (Se02) by Riley in 1931 that this
first selenium reagent was introduced into organic synthesis. Since that time
Se02 has been used for the oxidation of olefins and of carbonyl compounds in the
alpha position. The reaction was initially used for structure elucidation and later
as a key step in the synthesis of natural products. For the next forty years selenium
dioxide as well as elemental selenium and potassium selenocyanate were the only
selenium containing reagents used. Since 1973 and the pioneering work of
Barton, Clive, Reich, Sharpless, Sonoda, as well as of our laboratory several
inorganic and organic reagents containing an active selenium atom have been
proposed. These have proved to be particularly powerful and are being exten-
sively used in organic chemistry especially for the synthesis of natural products.
The aim of this Volume is to present the most frequently used selenium
containing reagents now available to chemists, to mention the scope as well as the
limitations of their reactions, and to compare those which possess similar
reactivities. We will present the reagents in the order of increasing oxidation level
around the selenium atom. Except for particularly relevant cases no effort has
been made to compare these reagents to those devoid of selenium but able to
perform the same transformations. References to related methods have however
V
Foreword
been inserted in the text and are preceded with a sign (@) whereas references
marked with an asterisk designate review articles.
In this Volume I we have restricted our review to those reactions which do not
involve isolatable selenium containing intermediates and therefore which are
operationally "one step" reactions.
On the other hand, transformations carried out in two or more separate steps
and which usually involve the isolation (and eventually the purification) of stable
organoselenium intermediates will be described in the forthcoming Volume II. In
this latter Volume II will also be included a detailed review of the preparation of
various selenium-based reagents.
We thank Drs J. L. Desiron and R. Menzies (Societe Generale des Minerais,
Bruxelles) who gave us invaluable informations on industrial aspects of selenium.
We are particularly grateful to Professor S. V. Ley (Imperial College, Lon-
don) who reviewed and corrected the entire manuscript.
We owe special thanks to Mrs Anne Krief for her patient contribution in
processing the references; to Mr Alain Burlet for his skill in drawing the Schemes
as well as to Mrs Evelyne Boca-Bastaits and Miss Veronique De Beys for their
courage and competence in typing the manuscript.
Namur, September 1987 Laszlo Hevesi
Alain Krief
VI
Contents
1. Introduction ............. . 1
1.1 Historical Review . . . . . . . . . . . . 1
1.2 Abundance and Distribution of Selenium 1
1.3 Selenium in Plants. . . . . . 1
1.4 Selenium Toxicity in Animals . . . . . . 2
1.5 Enzymic Role of Selenium ...... . 2
1.6 Ecological Aspects of Selenium in Human Health . 3
1.7 Extraction of Selenium . . . . . . . . . . . . . . 4
1.8 Industrial Uses of Selenium ........... . 5
1.9 Selenium: Structure, Physical and Chemical Properties 5
2. Reactions Involving Hydrogen Selenide, Selenols and Related
Compounds . .......................... . 12
2.1 Reactions Involving the Nucleophilicity of Hydrogen
Selenide, Selenols and Related Compounds. . . 12
2.1.1 N -de alkylation of Quaternary Ammonium Salts ... 12
2.1.2 N-dealkylation of Amines. . . . . . . . . . . . . . . 13
2.1.3 Dealkylation of Alkyl Aryl Ethers, -Sulfides and -Selenides . 15
2.1.4 Synthesis of Carboxylic Acids From Esters . . . . . . . . . 18
2.2 Reduction Reactions Involving Hydrogen Selenide, Selenols,
Selenocyanates, Triphenylphosphine Selenide and Related
Compounds ...................... . 20
2.2.1 Reduction of Benzyl Halides to Aryl Alkanes and of
Iodo- and Selenoketones to Ketones .. . . . . . . . . 21
2.2.2 Reduction of vic-Diheterosubstituted Alkanes to Alkenes 24
2.2.2.1 Selenolate Mediated Reduction of vic-Dihalogenoalkanes
and Bromohydrins to Olefins . . . . . . . . . . 24
2.2.2.2 Reduction of Epoxides and Thiiranes to Olefins. . . . . . . 27
2.2.3 Reduction of Disulfides to Thiolates ........... . 31
2.2.4 Reduction of Sulfoxides, Selenoxides and Telluroxides to
Sulfides, Selenides and Tellurides Respectively . . . . . . 32
2.2.5 Reduction of Nitro-, Nitroso-, Hydroxylamino-, Azo-,
Hydrazo-aromatic Compounds to Aromatic Amines and
Reduction of Afyldiazonium Salts to Hydrazinium Salts. . 35
2.2.6 Reduction of Schiff's Bases to Amines: Application to the
one Pot Reductive Amination of the Carbonyl Group . . . . 37
VII
Contents
2.2.7 Reduction of Aldehydes and Ketones to Alcohols . 38
2.2.8 Reduction of the Carbon-Carbon Double Bond of Enones 40
2.2.9 Reduction of Benzyl Selenides to Aryl Alkanes
and of Methylselenoacetals Derived Froin Aromatic
Carbonyl Compounds to Benzyl Methyl Selenides .. 41
2.3 Use of Copper (I) Benzeneselenolate . . . . . . . . . 43
2.3.1 As the Precursor of Mixed Alkyl Phenylselenocuprates 43
2.3.2 As a Catalyst in the Synthesis of (X-Selenoketones from
Selenolesters and Diazomethane . . . . . . . . . . . . . 44
2.4 Reduction of Dienes to Olefins With Dichloro Bis (Diphenyl
Selenide) Platinum (II) . . . . . . . . . . . . . . . . . . . . 44
3. Reactions Involving Metallic or Amorphous Selenium with
Organic Molecules . . . . . . . . . . . . . . . . . . . 46
3.1 Transformation of (Z) Alkenes to Their (E) Isomers . . . . . 46
3.2 Oxidation of Cyclic and Polycyclic Hydrocarbons and
Heterocycles to Aromatic Compounds Using Elemental Selenium 47
3.3 Oxido-reduction Reactions of Hydrocarbons . . . . . 52
3.4 Reactions Involving Carbon Monoxide and Catalytic
Amounts of Selenium . . . . . . . . . . . . . . . . . 52
3.4.1 Synthesis of Acylic Derivatives of Carbonic Acid . . . 53
3.4.2 Synthesis of Heterocycles Derived from Carbonic Acid 55
3.4.3 Synthesis of Carbonohydrazides, Semicarbazides,
Carbazates and Carbonates . . . . . . . . . . . . . . 56
3.4.4 Oxidation of Formates and Formamides to Carbonates and
Carbamates . . . . . . . . . . . . . . . . . . . . . . . . . 57
3.4.5 Synthesis of Hydrogen Selenide and Some of its Application 57
3.4.6 Oxidation of Hydrazine to Diimide: Application to the
Cis Hydrogenation of Olefins . . . . . . . . . . . . . . . . 58
3.4.7 Carbonylation of Alkyl Aryl Ketones to 1,3-Dicarbonyl
Compounds: Application to the Synthesis of 4-Hydroxycoumarins
58
4. Reactions Involving Selenoxides and Related Derivatives. 60
4.1 Reactions Involving Selenoxides . . . . . . . . . . . . 60
4.1.1 Oxidation of Sulfides, Amines and Acyl Hydrazines to
Sulfoxides, Aminoxides, and to Symmetrical Diacyl
Hydrazines, Respectively . . . . . . . . . . . . . . . . 60
4.1.2 Oxidation of Enediols to Dicarbonyl Compounds . . . . 62
4.1.3 Oxidative Conversion of Thiocarbonyl Compounds to
Carbonyl Compounds. . . . . . . . . . . . . . . . 64
4.1.4 Oxidation of Trivalent Phosphorus Compounds to
Their Oxides and of Thio- and Selenophosphorus
Derivatives to Their Oxygenated Analogues . fI . . 66
4.1.5 Oxidation of Olefins to vic-Glycols with Osmium
Tetroxide-Selenoxide Reagent . . . . . . . . . . . 68
VIII
Contents
4.2 Oxidation of Alcohols to Carbonyl Compounds with
DimethylselenidelN-chlorosuccinimide. . . . . . . . 69
4.3 Oxidative Conversion of sec-Benzylamines to Imines and
Tertiary Benzylamines to Iminium Salts by
Diphenylselenium Bis(t rifluoroacetate). . . . . . . . . . . 70
5. Reactions Involving Selenenyl Halides and Related Compounds 72
5.1 Allylic Halogenation of Olefins . . . . . . . . . . 72
5.2 Ring Expansion of 1 ,3-Dithiolans and 1,3-Dithians . . . . . .. 74
5.3 Oxidation of Alcohols to Carbonyl Compounds . . . . . . . .. 75
5.4 Synthesis of Oligonucleotides and Nucleoside Phosphoramidates. 75
6. Reactions Involving Benzeneseleninic Anhydride (BSA) and
Related Reagents . . . . . . . . . . . . . . . . . . . . . 76
6.1 Oxidation of Phenols, Pyrocatechols and Hydroquinones . 76
6.2 Dehydrogenation of Ketones to Enones and Dienones 81
6.3 Dehydrogenation of Lactones and Lactams to
0:, j3-Unsaturated Compounds. . . . . . . . . . . . . 85
6.4 Oxidation of Alcohols to Carbonyl Compounds or to
Enones and Dienones . . . . . . . . . . . . . . . . 86
6.4.1 WithBSA. . . . . . . . . . . . . . . . . . . . . . . . 86
6.4.2 With Diphenyldiselenide and t-Butyl Hydroperoxide . . 87
6.5 Oxidative Conversion of Thiols to Disulfides, Sulfides to
Sulfoxides and of Phosphines to Phosphinoxides 90
6.6 Oxidation of Amines . . . . . 90
6.7 Oxidation of Hydrazines .. . . . . . . . . . . 93
6.8 OxidationofHydroxylamines. . . . . . . . . . 95
6.9 Oxidation of the Alkyl Chain of Aromatic and
Heteroaromatic Compounds . . . . . . . . 95
6.10 Regeneration of Carbonyl Compounds . . . 97
6.10.1 From Thioketones, Hydrazones and Oximes 97
6.10.2 From Thioacetals and Selenoacetals. . . . . 99
6.10.3 From Xanthates, Thioesters, Thiocarbonates, Thioamides
and Their Telluro Analogues . . . . . . . . . . . . . . . 100
6.11 Synthesis of o:-Selenocarbonyl Compounds from BSA and 101
6.11.1 Vinyl Sulfides and Vinyl Selenides. . . . . . . 101
6.11.2 Allyl Alcohols. . . . . . . . . . . . . . . . . 102
6.12 Synthesis of Allyl Alcohols from Allyl Silanes . 102
7. Reactions Involving Benzeneseleninyl Halides 104
7.1 Oxidation of Aldoximes to Nitriles . . . . . . 104
7.2 Oxidation of Amines . . . . . . . . . . . . . 104
7.3 Dehydrogenation of Carbonyl Compounds to Enones . 105
IX
Contents
8. Reactions Involving Perseleninic Acids 106
8.1 Oxidation of Olefins to Epoxides . . . . . . . . . . . . 106
8.2 Baeyer-Villiger Type Oxidation of Ketones to Esters
and Lactones . . . . . . . . . . . . . . . . . . . . . 111
8.3 Oxidation of Selenides to Selenoxides and Selenones
and of Sulfides to Sulfoxides or Sulfones . 113
9. Selenium Dioxide Oxidations . . . . . . 115
9.1 Reactivity of Se02 with Alkenes. . . . . 116
9.1.1 Oxidation of Alkenes with Se02 or Se021t-Bu02H 116
9.1.1.1 Scope of Limitation . . . . .. 116
9.1.1.2 Regiochemistry . . . . . . . . 129
9.1.1.3 Stereochemical Considerations 133
9.1.1.4 Mechanistic Considerations . . 133
9.1.1.5 Use of the Reaction for the Synthesis of Complex Molecules
and as a Key Step in the Total Synthesis of Natural Products. . 135
9.1.2 Diol Formation from Alkenes and Se02/H202 or Se02/H2S04 136
9.1.3 Oxidation of Functionalized Olefins With Se02 . . . . 136
9.2 Reactivity of Se02 Towards Acetylenic Hydrocarbons 140
9.3 Reactivity of Se02 with Carbonyl Compounds 144
9.3.1 Reactions Involving Se02 . . . . . . . . . . . . . . . 144
9.3.1.1 Scope and Limitation . . . . . . . . . . . . . . . . . 144
9.3.1.2 Oxidation of Carbonyl Compounds to (X-Dicarbonyl Compounds . 146
9.3.1.3 Dehydrogenation of Carbonyl Compounds . . . . . . . . 150
9.3.1.4 Acetalisation of Carbonyl Compounds Catalyzed by Se02 . . 155
9.3.2 Oxidation of Carbonyl Compounds with Se021H202
- Synthesis of Carboxylic Acids from Aldehydes and Ketones . 156
9.3.2.1 Reaction of Se02/H202 with Ketones . . . . . . 156
9.3.2.2 Reaction of Se02/H202 with Aldehydes. . . . . 162
9.4 Oxidation of the Alkyl Chain of Aromatic and
Heteroaromatic Compounds . . . . . . . . . . 162
9.4.1 Synthesis of Aryl Carbonyl Compounds. . . . . 163
9.4.2 Aromatisation of Cyclic and Heterocyclic Compounds 169
9.5 Oxidation of Benzylic and Allylic Alcohols . . . . . . 169
9.6 Oxidation of Hydrazones, Imines, Oximes and Semicarbazones 170
9.7 Conversion of Thio- and Selenocarbonyl Compounds
to Carbonyl Compounds . . . . . . . . . . . . . . 177
9.8 Reactions of Nitroalkanes: Synthesis of N-hydroxy
Carboxamides and Nitriles . . . . . . . . . . . . . 177
9.9 Synthesis of Olefins from Phosphorus Ylides and Diazoalkanes . 177
9.10 Reaction of Se02 with Phosphines, Arsines, Stibines
and Related Compounds . . . 178
9.11 Reaction with Hydrazines. . . 179
9.12 Reaction with Organometallics 180
x
Contents
10. Reactions ofimidoselenium Compounds . . . . . 181
10.1 With Alkenes and Alkynes: Synthesis of Allylic
and Propargylic Amines. . . . . . . . . . . . 181
10.2 With Dienes: Synthesis of Cis Diaminoalkanes . 184
11. Reactions Involving Selenium Oxychloride and
Selenium Tetrahalides ...... . 187
11.1 Reactivity of Selenium Oxychloride. . . . . . . 187
11.2 Reactivity of Selenium Tetrafluoride . . . . . . 187
11.2.1 Synthesis of Geminal Difluoroalkanes from Aldehydes
and Ketones. . . . . . . . . . . . . . . . 187
11.2.2 Synthesis of Alkylfluorides from Alcohols. 188
11.3 Reactivity of Selenium Tetrachloride 189
References . . 190
Subject Index. 205
XI