Science of Synthesis: Houben-Weyl Methods of Molecular Transformations Vol. 47b E-Book

• Herausgeber: Thieme
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch
• Veröffentlichungsjahr: 2014

Beschreibung

Science of Synthesis: Houben-Weyl Methods of Molecular Transformations is the entirely new edition of the acclaimed reference series Houben-Weyl, the standard synthetic chemistry resource since 1909. This new edition is published in English and will comprise 48 volumes published between the years 2000 and 2008.

Science of Synthesis is a quality reference work developed by a highly esteemed editorial board to provide a comprehensive and critical selection of reliable organic and organometallic synthetic methods. This unique resource is designed to be the first point of reference when searching for a synthesis strategy.

• Contains the expertise of presently 400 leading chemists worldwide
• Critically evaluates the preparative applicability and significance of the synthetic methods
• Discusses relevant background information and provides detailed experimental procedures

For full information on the Science of Synthesis series, visit the Science of Synthesis Homepage.

Leseprobe

Science of Synthesis

Science of Synthesis is the authoritative and comprehensive reference work for the entire field of organic and organometallic synthesis.

Science of Synthesis presents the important synthetic methods for all classes of compounds and includes:

Methods critically evaluated by leading scientists

Background information and detailed experimental procedures

Schemes and tables which illustrate the reaction scope

Preface

As our understanding of the natural world increases, we begin to understand complex phenomena at molecular levels. This level of understanding allows for the design of molecular entities for functions ranging from material science to biology. Such design requires synthesis and, as the structures increase in complexity as a necessity for specificity, puts increasing demands on the level of sophistication of the synthetic methods. Such needs stimulate the improvement of existing methods and, more importantly, the development of new methods. As scientists confront the synthetic problems posed by the molecular targets, they require access to a source of reliable synthetic information. Thus, the need for a new, comprehensive, and critical treatment of synthetic chemistry has become apparent. To meet this challenge, an entirely new edition of the esteemed reference work Houben–Weyl Methods of Organic Chemistry will be published starting in the year 2000.

To reflect the new broader need and focus, this new edition has a new title, Science of Synthesis, Houben–Weyl Methods of Molecular Transformations. Science of Synthesis will benefit from more than 90 years of experience and will continue the tradition of excellence in publishing synthetic chemistry reference works. Science of Synthesis will be a balanced and critical reference work produced by the collaborative efforts of chemists, from both industry and academia, selected by the editorial board. All published results from journals, books, and patent literature from the early 1800s until the year of publication will be considered by our authors, who are among the leading experts in their field. The 48 volumes of Science of Synthesis will provide chemists with the most reliable methods to solve their synthesis problems. Science of Synthesis will be updated periodically and will become a prime source of information for chemists in the 21st century.

Science of Synthesis will be organized in a logical hierarchical system based on the target molecule to be synthesized. The critical coverage of methods will be supported by information intended to help the user choose the most suitable method for their application, thus providing a strong foundation from which to develop a successful synthetic route. Within each category of product, illuminating background information such as history, nomenclature, structure, stability, reactivity, properties, safety, and environmental aspects will be discussed along with a detailed selection of reliable methods. Each method and variation will be accompanied by reaction schemes, tables of examples, experimental procedures, and a background discussion of the scope and limitations of the reaction described.

The policy of the editorial board is to make Science of Synthesis the ultimate tool for the synthetic chemist in the 21st century.

We would like to thank all of our authors for submitting contributions of such outstanding quality, and also for the dedication and commitment they have shown throughout the entire editorial process.

October 2000

The Editorial Board

D. Bellus (Basel, Switzerland)

E. N. Jacobsen (Cambridge, USA)

S. V. Ley (Cambridge, UK)

R. Noyori (Nagoya, Japan)

M. Regitz (Kaiserslautern, Germany)

P. J. Reider (New Jersey, USA)

E. Schaumann (Clausthal-Zellerfeld, Germany)

I. Shinkai (Tsukuba, Japan)

E. J. Thomas (Manchester, UK)

B. M. Trost (Stanford, USA)

Volume Editor’s Preface

This volume of Science of Synthesis, dealing with the various approaches to alkenes, is meant to aid researchers around the world who are engaged in developing synthetic approaches to new chemical entities or improving existing routes to known compounds of any importance. The carbon—carbon double bond with which every alkene is endowed, be it a hydrocarbon or not, is one of the most versatile functional groups in an organic molecule. Considering the multitude of other functionalities with which most methods for the synthesis of alkenes are compatible, alkenes gain even more importance in organic synthesis. The classical methods of alkene preparation comprise mainly elimination reactions of various kinds. However, the development of alkene syntheses, even of the eliminations, has never stopped. On top of these developments, the classical approaches have been supplemented with new elimination methods, and the arsenal of tools has been broadened particularly by the various carbonyl alkenation methodologies, the multitude of metal-catalyzed and metal-mediated cross couplings, including the Mizoroki–Heck reaction, as well as the modern ways of converting simple alkenes into more complex ones by the so-called metathesis principle. The development of these latter methods especially is continuing at a rapid rate, creating new improvements with wider applicability every year. Thus, this volume on alkenes covers the whole spectrum of alkene syntheses, and their applications, that have been discovered in more than 130 years.

As the volume editor I have enjoyed once again collaborating with a highly competent team of scientific editors, copy editors, artwork producers, and others at Thieme, directed by the managing editor Dr. M. Fiona Shortt de Hernandez. Their professionalism and impressively great care in their permanent engagement has brought forward a quality product that is virtually unequalled. It goes without saying that all of this would not have been achieved without the tremendous efforts of all of the authors who have contributed to this volume. Finally, I would like to thank Prof. Dr. Eric N. Jacobsen, the responsible member of the Editorial Board, and Dr. Joe P. Richmond, the independent advisor for Science of Synthesis, for their invaluable help at the beginning of this endeavour, especially in organizing the table of contents and putting together a list of competent authors.

Göttingen, October 2009

Volume Editor

Armin de Meijere

Volume 47b: Alkenes

Preface

Volume Editor’s Preface

Table of Contents

47.1 Product Class 1: Alkenes

47.1.3 Synthesis by Pericyclic Reactions

47.1.3.1 Diels–Alder Reactions

F. Fringuelli, O. Piermatti, F. Pizzo, and L. Vaccaro

47.1.3.2 Ene Reactions

P. Chiu and S. K. Lam

47.1.3.3 Synthesis by Electrocyclic Reactions

J.-M. Lu, L.-X. Shao, and M. Shi

47.1.4 Synthesis by Elimination Reactions

R. R. Kostikov, A. F. Khlebnikov, and V. V. Sokolov

47.1.5 Synthesis from Alkynes by Addition Reactions

47.1.5.1 [2 + 2]-Cycloaddition Reactions

V. V. Razin

47.1.5.2 Hydrogenation Reactions

K.-M. Roy

47.1.5.3 Hydrometalation and Subsequent Coupling Reactions

E. Negishi and G. Wang

47.1.5.4 Carbometalation and Subsequent Coupling Reactions

E. Negishi and G. Wang

47.1.6 Synthesis from Arenes and Polyenes by Addition Reactions

R. A. Aitken and K. M. Aitken

47.1.7 Synthesis by Isomerization

M. Yus and F. Foubelo

47.1.8 Synthesis from Other Alkenes without Isomerization

M. Yus and F. Foubelo

47.2 Product Class 2: Cyclopropenes

M. S. Baird

47.3 Product Class 3: Nonconjugated Di-, Tri-, and Oligoenes

K.-M. Roy

Keyword Index

Author Index

Abbreviations

Table of Contents

47.1 Product Class 1: Alkenes

47.1.3 Synthesis by Pericyclic Reactions

47.1.3.1 Diels–Alder Reactions

F. Fringuelli, O. Piermatti, F. Pizzo, and L. Vaccaro

47.1.3.1 Diels–Alder Reactions

47.1.3.1.1 Thermal Diels–Alder Reactions

47.1.3.1.1.1 Method 1: Reactions of Carbonyl Dienophiles

47.1.3.1.1.1.1 Variation 1: Synthesis of Cyclohexenecarbaldehydes

47.1.3.1.1.1.2 Variation 2: Synthesis of Acetylcyclohexenes

47.1.3.1.1.1.3 Variation 3: Synthesis of Cyclohexenecarboxylic Acids and Alkyl Cyclohexenecarboxylates

47.1.3.1.1.1.4 Variation 4: Synthesis of Dialkyl Cyclohexenedicarboxylates

47.1.3.1.1.1.5 Variation 5: Synthesis of Cyclohexenecarboxylic Acids, Cyclohexenecarbonyl Chlorides, Cyclohexenecarboxamides, and Cyclohexenyl Silyl Ketones

47.1.3.1.1.1.6 Variation 6: Synthesis of Cyclohexenes Fused to Carbo- and Heterocycles

47.1.3.1.1.1.7 Variation 7: Synthesis of Bridged Cyclohexenes

47.1.3.1.1.2 Method 2: Reactions of Other Vinyl Dienophiles

47.1.3.1.1.2.1 Variation 1: Synthesis of Nitrocyclohexenes

47.1.3.1.1.2.2 Variation 2: Synthesis of Cyclohexenylboranes

47.1.3.1.1.2.3 Variation 3: Synthesis of Cyclohexenecarbonitriles

47.1.3.1.1.2.4 Variation 4: Synthesis of Cyclohex-3-enyl Phenyl Sulfones

47.1.3.1.1.2.5 Variation 5: Synthesis of (Hydroxyalkyl)cyclohexenes

47.1.3.1.1.2.6 Variation 6: Synthesis of Cyclohexenes from Unusual Dienophiles

47.1.3.1.1.3 Method 3: Synthesis of Cyclohexenyl-Substituted Fischer Carbene Complexes

47.1.3.1.1.4 Method 4: Synthetic Applications of Diels–Alder Reactions

47.1.3.1.2 Catalyzed Diels–Alder Reactions in Conventional Organic Media

47.1.3.1.2.1 Method 1: Reactions Using Classic Lewis Acid Catalysts

47.1.3.1.2.2 Method 2: Reactions Using Chiral Lewis Acid Catalysts

47.1.3.1.2.3 Method 3: Reactions Using Brønsted Acid Catalysts

47.1.3.1.2.4 Method 4: Reactions Using Chiral Organocatalysts

47.1.3.1.2.5 Method 5: Lewis Acid Catalyzed Diels–Alder Reactions of Chiral Dienophiles or Dienes

47.1.3.1.2.5.1 Variation 1: With Chiral Dienophiles

47.1.3.1.2.5.2 Variation 2: With Chiral Dienes

47.1.3.1.2.6 Method 6: Reactions Using Heterogeneous Catalysts

47.1.3.1.3 Diels–Alder Reactions in Unconventional Media

47.1.3.1.3.1 Method 1: Reactions in Water

47.1.3.1.3.1.1 Variation 1: Without a Catalyst

47.1.3.1.3.1.2 Variation 2: With a Lewis Acid Catalyst

47.1.3.1.3.1.3 Variation 3: With Organocatalysts

47.1.3.1.3.1.4 Variation 4: In Supercritical Water

47.1.3.1.3.1.5 Variation 5: In Pseudo-Biological Systems or Promoted by Biocatalysts

47.1.3.1.3.2 Method 2: Reactions in Nonaqueous Solvents and Their Salt Solutions

47.1.3.1.3.3 Method 3: Reactions in Ionic Liquids

47.1.3.1.4 Diels–Alder Reactions Induced by Other Physical Means

47.1.3.1.4.1 Method 1: Diels–Alder Reactions Promoted by Microwave Irradiation

47.1.3.1.4.2 Method 2: Diels–Alder Reactions Promoted by High Pressure

47.1.3.1.4.3 Method 3: Ultrasound-Assisted Diels–Alder Reactions

47.1.3.1.4.4 Method 4: Photoinduced Diels–Alder Reactions

47.1.3.2 Ene Reactions

P. Chiu and S. K. Lam

47.1.3.2 Ene Reactions

47.1.3.2.1 Method 1: Thermal Ene Reactions

47.1.3.2.1.1 Variation 1: Intermolecular Ene Reactions

47.1.3.2.1.2 Variation 2: Reactions of 1,n-Dienes

47.1.3.2.2 Method 2: Metallo-Ene Reactions of Allylmetal Species

47.1.3.2.2.1 Variation 1: Reactions Using Alkenes as Enophiles, Followed by Protonolysis

47.1.3.2.2.2 Variation 2: Reactions Using Vinylmetals as Enophiles, Followed by Protonolysis

47.1.3.2.3 Method 3: Metal-Catalyzed Metallo-Ene Reactions

47.1.3.2.3.1 Variation 1: Palladium-Catalyzed Metallo-Ene Reactions Terminated by Transmetalation and Protonation

47.1.3.2.3.2 Variation 2: Palladium-Catalyzed Metallo-Ene Reactions Terminated by Hydride Capture

47.1.3.2.4 Method 4: Metal-Catalyzed Rearrangements

47.1.3.2.5 Method 5: Retro-Ene Reactions of All-Carbon Ene Adducts

47.1.3.2.5.1 Variation 1: Reactions of Homoallylic Alcohols

47.1.3.2.5.2 Variation 2: Reactions of Allyldiazenes

47.1.3.2.5.3 Variation 3: Reactions of Alk-2-enesulfinic Acid Derivatives

47.1.3.3 Synthesis by Electrocyclic Reactions

J.-M. Lu, L.-X. Shao, and M. Shi

47.1.3.3 Synthesis by Electrocyclic Reactions

47.1.3.3.1 Method 1: Rearrangement of 4π-Electron Systems

47.1.3.3.1.1 Variation 1: Rearrangement of Acyclic 1,3-Dienes

47.1.3.3.1.2 Variation 2: Rearrangement of Cyclic 1,3-Dienes

47.1.3.3.1.3 Variation 3: Rearrangement of 1,2-Dimethylene-Substituted Cycloalkanes

47.1.3.3.1.4 Variation 4: Rearrangement of 1,2-Dimethylene-Substituted Heterocycles

47.1.3.3.2 Method 2: Rearrangement of 2π-Electron Systems

47.1.3.3.2.1 Variation 1: Solvolysis of Chlorocyclopropanes

47.1.3.3.2.2 Variation 2: Solvolysis of Cyclopropyl 4-Toluenesulfonates

47.1.3.3.3 Method 3: Cope Rearrangement

47.1.3.3.3.1 Variation 1: Rearrangement of Acyclic 1,5-Dienes

47.1.3.3.3.2 Variation 2: Rearrangement of Cyclic 1,5-Dienes

47.1.3.3.3.3 Variation 3: Rearrangement of 1,2-Divinylcycloalkanes

47.1.4 Synthesis by Elimination Reactions

R. R. Kostikov, A. F. Khlebnikov, and V. V. Sokolov

47.1.4 Synthesis by Elimination Reactions

47.1.4.1 Method 1: Synthesis by Decarbonylative Elimination

47.1.4.1.1 Variation 1: Oxidative Decarboxylation of Carboxylic Acids

47.1.4.1.2 Variation 2: Oxidative Decarboxylation of Acid Anhydrides

47.1.4.1.3 Variation 3: Decarbonylation of Acid Halides and Aldehydes

47.1.4.1.4 Variation 4: Decarbonylative Reactions of β,γ-Unsaturated Acids

47.1.4.1.5 Variation 5: Decarbonylative Elimination from β-Halo- and β-Hydroxycarboxylic Acids

47.1.4.1.6 Variation 6: Fragmentation of β-Lactones

47.1.4.1.7 Variation 7: Fragmentation of 1,3-Diketones

47.1.4.1.8 Variation 8: Grob Fragmentation

47.1.4.2 Method 2: Oxidative Decarboxylation of Dicarboxylic Acid Derivatives

47.1.4.2.1 Variation 1: Oxidative Decarboxylation of 1,2-Dicarboxylic Acid Derivatives

47.1.4.2.2 Variation 2: Oxidative Decarboxylation of 1,3-Dicarboxylic Acids

47.1.4.3 Method 3: Base-Catalyzed and Solvolytic HX Elimination

47.1.4.3.1 Variation 1: Elimination from Alkyl Halides

47.1.4.3.2 Variation 2: Elimination from Ethers and Sulfides

47.1.4.3.3 Variation 3: Elimination from Metal Alkoxides

47.1.4.3.4 Variation 4: Elimination from Ammonium Salts

47.1.4.3.5 Variation 5: Elimination from Sulfonium Salts

47.1.4.3.6 Variation 6: Solvolytic and Base-Catalyzed Elimination from 4-Toluenesulfonates and Other Sulfonates

47.1.4.4 Method 4: Acid-Catalyzed HX Elimination

47.1.4.4.1 Variation 1: Acid-Catalyzed Dehydration of Alcohols

47.1.4.4.2 Variation 2: Dehydration of Alcohols Using Lewis Acids and Heterogeneous Catalysts

47.1.4.4.3 Variation 3: Dehydration of Alcohols with Other Systems

47.1.4.5 Method 5: Pyrolytic HX Elimination

47.1.4.5.1 Variation 1: Pyrolysis of Alkyl Halides

47.1.4.5.2 Variation 2: Pyrolysis of Esters

47.1.4.5.3 Variation 3: Pyrolysis of Xanthates, Thiocarbamates, Thiophosphates, Arenesulfonates, Sulfamates, and Sulfuranes

47.1.4.5.4 Variation 4: Cope Elimination from N-Oxides

47.1.4.5.5 Variation 5: Thermolytic Elimination from Ammonium Hydroxides

47.1.4.5.6 Variation 6: Thermolytic Elimination from Phosphonium Salts

47.1.4.5.7 Variation 7: Thermolytic Elimination from Alkyl Selenoxides

47.1.4.5.8 Variation 8: Thermolytic Dehydration of Alcohols in Dimethyl Sulfoxide or Hexamethylphosphoric Triamide

47.1.4.6 Method 6: Reductive Elimination from Halohydrins and Their Esters or Ethers

47.1.4.6.1 Variation 1: Dehalogenation of Vicinal Dihalides

47.1.4.6.2 Variation 2: Elimination from Halohydrins

47.1.4.6.3 Variation 3: Elimination from Halohydrin Esters

47.1.4.6.4 Variation 4: Elimination from Halohydrin Ethers

47.1.4.6.5 Variation 5: Elimination from vic-Diols

47.1.4.6.6 Variation 6: Elimination from vic-Diol Disulfonates

47.1.4.7 Method 7: Reductive Elimination of X2 from Fragments of the Type CX2—CH2

47.1.4.7.1 Variation 1: Dehalogenation of Geminal Dihalides

47.1.4.7.2 Variation 2: Elimination of Nitrogen from Diazo Compounds

47.1.4.8 Method 8: Reductive Extrusions from Three- to Five-Membered Heterocycles

47.1.4.8.1 Variation 1: From Oxiranes

47.1.4.8.2 Variation 2: From Thiiranes and Thiirane 1,1-Dioxides

47.1.4.8.3 Variation 3: Ramberg–Bäcklund Reaction

47.1.4.8.4 Variation 4: From Aziridines

47.1.4.8.5 Variation 5: From 1,3-Dioxolane- and 1,3-Dithiolane-2-thiones

47.1.4.8.6 Variation 6: From 2-Alkoxy- and 2-(Dimethylamino)-1,3-dioxolanes

47.1.4.9 Method 9: Reactions of Ketone (Arylsulfonyl)hydrazones

47.1.4.9.1 Variation 1: The Bamford–Stevens Reaction

47.1.4.9.2 Variation 2: The Shapiro Reaction

47.1.4.9.3 Variation 3: Sequential Transformations Based on the Shapiro Reaction

47.1.4.10 Method 10: Dehydrogenation of CH2—CH2 Fragments

47.1.5 Synthesis from Alkynes by Addition Reactions

47.1.5.1 [2 + 2]-Cycloaddition Reactions

V. V. Razin

47.1.5.1 [2 + 2]-Cycloaddition Reactions

47.1.5.1.1 Method 1: Photochemical and Microwave-Assisted Reactions

47.1.5.1.1.1 Variation 1: From Diphenylacetylene

47.1.5.1.1.2 Variation 2: From Diynes, Triynes, and Vinylacetylene

47.1.5.1.1.3 Variation 3: Intramolecular Reactions

47.1.5.1.2 Method 2: Thermocatalytic Reactions

47.1.5.1.2.1 Variation 1: Lewis Acid Catalyzed [2 + 2] Cycloadditions

47.1.5.1.2.2 Variation 2: Reactions Catalyzed by Nickel, Ruthenium, and Cobalt Complexes

47.1.5.1.2.3 Variation 3: Zirconocene-Catalyzed Cyclobutene Formation

47.1.5.2 Hydrogenation Reactions

K.-M. Roy

47.1.5.2 Hydrogenation Reactions

47.1.5.2.1 Method 1: Catalytic Hydrogenation

47.1.5.2.2 Method 2: Chemical Reduction

47.1.5.2.2.1 Variation 1: Reduction with Metals

47.1.5.2.2.2 Variation 2: Reduction by Hydrometalation–Protodemetalation

47.1.5.3 Hydrometalation and Subsequent Coupling Reactions

E. Negishi and G. Wang

47.1.5.3 Hydrometalation and Subsequent Coupling Reactions

47.1.5.3.1 Method 1: syn-Hydrometalation Reactions of Alkynes Producing E-β-Mono-, syn-α,β-Di-, and anti-α,β-Disubstituted Alkenylmetals

47.1.5.3.1.1 Variation 1: syn-Hydrometalation of Alkynes Involving Group 1, 2, 11, and 12 Metals

47.1.5.3.1.2 Variation 2: Hydroboration of Alkynes

47.1.5.3.1.3 Variation 3: Substitution of Boron in the Hydroboration Products with Hydrogen and Heteroatoms

47.1.5.3.1.4 Variation 4: C—C Bond-Forming Reactions That Are Unique to Organoboranes

47.1.5.3.1.5 Variation 5: Hydroalumination and Hydrozirconation of Alkynes

47.1.5.3.1.6 Variation 6: Substitution of the Metal in Alkenylaluminum and Alkenylzirconium Compounds with Hydrogen or Deuterium, Halogens, Other Heteroatoms, Metals, and Carbon

47.1.5.3.2 Method 2: anti-Hydrometalation Reactions of Alkynes Producing Z-β-Mono- and anti-α,β-Disubstituted Alkenylmetals

47.1.5.3.2.1 Variation 1: anti-Hydroalumination of Alkynes with Hydroaluminates

47.1.5.3.2.2 Variation 2: Other anti-Hydrometalation Reactions of Alkynes

47.1.5.3.2.3 Variation 3: Useful Alternatives to anti-Hydrometalation of Alkynes

47.1.5.3.3 Method 3: Palladium-Catalyzed Cross-Coupling Reactions of Alkenylmetals or Alkenyl Electrophiles Prepared by Alkyne Hydrometalation

47.1.5.3.3.1 Variation 1: 1,2-Disubstituted E-Alkenes via β-Monosubstituted E-Alkenyl Derivatives

47.1.5.3.3.2 Variation 2: 1,2-Disubstituted E-Alkenes via β-Monosubstituted E-Alkenyl Derivatives Preparable by Methods Other Than Hydrometalation

47.1.5.3.3.3 Variation 3: 1,2-Disubstituted Z-Alkenes via β-Monosubstituted Z-Alkenyl Derivatives Preparable by Alkyne Hydrometalation, Ethyne Carbocupration, and Other Methods

47.1.5.3.3.4 Variation 4: Trisubstituted Alkenes via syn-α,β-Disubstituted Alkenyl Derivatives Preparable by Alkyne syn-Hydrometalation and Other Methods

47.1.5.3.3.5 Variation 5: Trisubstituted Alkenes via anti-α,β-Disubstituted Alkenyl Derivatives Prepared by Alkyne syn- or anti-Hydrometalation and Other Methods Not Involving Elementometalation

47.1.5.4 Carbometalation and Subsequent Coupling Reactions

E. Negishi and G. Wang

47.1.5.4 Carbometalation and Subsequent Coupling Reactions

47.1.5.4.1 Method 1: Syntheses of Trisubstituted Alkenes via Zirconium-Catalyzed syn-Carboalumination of Alkynes

47.1.5.4.2 Method 2: Syntheses of Trisubstituted Alkenes by Carbocupration of Alkynes

47.1.5.4.2.1 Variation 1: syn-Carbocupration of Alkynes

47.1.5.4.2.2 Variation 2: Copper-Catalyzed anti-Carbomagnesiation of Propargyl Alcohols

47.1.5.4.3 Method 3: Synthesis of Trisubstituted Alkenes via syn-Haloboration of Alkynes

47.1.5.4.4 Method 4: Synthesis of Trisubstituted Alkenes via β,β-Disubstituted Alkenyl Derivatives Prepared by Miscellaneous Other Methods

47.1.5.4.5 Method 5: Synthesis of Tetrasubstituted Alkenes via Trisubstituted Alkenyl Derivatives

47.1.6 Synthesis from Arenes and Polyenes by Addition Reactions

R. A. Aitken and K. M. Aitken

47.1.6 Synthesis from Arenes and Polyenes by Addition Reactions

47.1.6.1 Synthesis from Arenes

47.1.6.1.1 Method 1: Reduction by Metals in Liquid Ammonia

47.1.6.1.1.1 Variation 1: Reduction by Lithium and Added Ethanol

47.1.6.1.1.2 Variation 2: Reduction by Sodium and Added Ethanol

47.1.6.1.1.3 Variation 3: Reduction by Potassium and Added tert-Butyl Alcohol

47.1.6.1.1.4 Variation 4: Reduction by Calcium

47.1.6.1.2 Method 2: Reduction by Lithium and Alkylamines

47.1.6.1.2.1 Variation 1: Reduction in Methylamine or Ethylamine

47.1.6.1.2.2 Variation 2: Reduction in Ethylenediamine

47.1.6.1.2.3 Variation 3: Reduction in Mixed-Amine Systems

47.1.6.1.3 Method 3: Electrochemical Reduction in Methylamine

47.1.6.1.4 Method 4: Reduction by Sodium and tert-Butyl Alcohol

47.1.6.2 Synthesis from 1,2-Dienes (Allenes)

47.1.6.2.1 Method 1: Reduction by Addition of Hydrogen

47.1.6.2.1.1 Variation 1: Catalytic Hydrogenation

47.1.6.2.1.2 Variation 2: Transfer Hydrogenation Using Ammonium Formate

47.1.6.2.1.3 Variation 3: Reduction by Lithium or Sodium in Liquid Ammonia

47.1.6.2.1.4 Variation 4: Reduction by Sodium and Ethanol

47.1.6.2.1.5 Variation 5: Reduction by the Zinc–Copper Couple

47.1.6.2.1.6 Variation 6: Reduction by Diimide

47.1.6.2.1.7 Variation 7: Reduction by Red Phosphorus and Hydriodic Acid

47.1.6.2.1.8 Variation 8: Reduction by Borane

47.1.6.2.1.9 Variation 9: Reduction by Aluminum Hydrides

47.1.6.2.1.10 Variation 10: Reduction by Baker’s Yeast

47.1.6.2.1.11 Variation 11: Miscellaneous Variations

47.1.6.2.2 Method 2: Synthesis by Hydrocarbonation (Addition of Carbon and Hydrogen)

47.1.6.2.2.1 Variation 1: Hydrocarbonation Using a Grignard Reagent

47.1.6.2.2.2 Variation 2: Hydrocarbonation Using Arylboronates

47.1.6.2.2.3 Variation 3: Hydrocarbonation Using Stabilized Carbanions

47.1.6.2.2.4 Variation 4: Hydrocarbonation by Hydrozirconation Followed by Zinc-Mediated Claisen Rearrangement

47.1.6.2.2.5 Variation 5: Hydrocarbonation by Reductive Coupling to Carbonyl Compounds

47.1.6.3 Synthesis from 1,3-Dienes or Fully Conjugated Polyenes

47.1.6.3.1 Synthesis by Addition of Hydrogen

47.1.6.3.1.1 Method 1: Catalytic Hydrogenation

47.1.6.3.1.1.1 Variation 1: Hydrogenation Using Chromium or Molybdenum Catalysts

47.1.6.3.1.1.2 Variation 2: Hydrogenation Using Nickel Catalysts

47.1.6.3.1.1.3 Variation 3: Hydrogenation Using Palladium Catalysts

47.1.6.3.1.1.4 Variation 4: Hydrogenation Using Platinum Catalysts

47.1.6.3.1.1.5 Variation 5: Hydrogenation Using Other Metal Catalysts

47.1.6.3.1.2 Method 2: Dissolving Metal Reduction

47.1.6.3.1.2.1 Variation 1: Reduction by Lithium and Ammonia

47.1.6.3.1.2.2 Variation 2: Reduction by Sodium and Ammonia

47.1.6.3.1.2.3 Variation 3: Reduction by Sodium Amalgam

47.1.6.3.1.2.4 Variation 4: Reduction by Sodium and an Alcohol

47.1.6.3.1.2.5 Variation 5: Reduction by Magnesium

47.1.6.3.1.2.6 Variation 6: Reduction by Aluminum Amalgam

47.1.6.3.1.2.7 Variation 7: Reduction by Zinc and Acetic Acid

47.1.6.3.1.3 Method 3: Reduction by Sodium Borohydride with Iodine or Disodium Tetracyanonickelate

47.1.6.3.1.4 Method 4: Reduction by Diisobutylaluminum Hydride

47.1.6.3.1.5 Method 5: Reduction by Platinum-Catalyzed Hydrosilylation

47.1.6.3.1.6 Method 6: Reduction by Diimide

47.1.6.3.1.7 Method 7: Reduction by Sodium Dithionite

47.1.6.3.1.8 Method 8: Reduction by Zirconocene and Hydrochloric Acid

47.1.6.3.1.9 Method 9: Reduction by Vanadium(II) and Pyrocatechol

47.1.6.3.1.10 Method 10: Reduction by Samarium and Water

47.1.6.3.1.11 Method 11: Electrochemical Reduction

47.1.6.3.1.12 Method 12: Reduction by Nicotinamide Adenine Dinucleotide Model Dihydropyridines

47.1.6.3.1.13 Method 13: Reduction by Yeasts

47.1.6.3.2 Synthesis by Hydrocarbonation (Addition of Carbon and Hydrogen)

47.1.6.3.2.1 Method 1: Hydrocarbonation Using Alkyllithium Reagents

47.1.6.3.2.2 Method 2: Hydrocarbonation Using Alkylsodium Reagents

47.1.6.3.2.3 Method 3: Hydrocarbonation Using Organometallic Reagents

47.1.6.3.2.4 Method 4: Hydrocarbonation Using Nitroalkane Anions

47.1.6.3.2.5 Method 5: Hydrocarbonation Using Stabilized Carbanions

47.1.6.3.2.6 Method 6: Hydrocarbonation by Reductive Coupling to Carbonyl Compounds, Imines, or Alkenes

47.1.6.3.3 Synthesis by Carbonation (Formation of Two C—C Bonds)

47.1.6.3.3.1 Method 1: Carbonation Using an Alkyl- or Aryllithium and a Haloalkane

47.1.6.3.3.2 Method 2: Carbonation Using a Grignard Reagent Followed by Carbon Dioxide

47.1.6.3.3.3 Method 3: Carbonation Using a Nickel-Catalyst with Trimethylborane or Dimethylzinc and an Aldehyde

47.1.6.3.3.4 Method 4: Carbonation Using an Alkylcopper Reagent Followed by a Carbonyl or Haloalkane Electrophile

47.1.6.3.3.5 Method 5: Carbonation Using an Acyl(carbonyl)cobalt Reagent and a Stabilized Carbanion

47.1.6.3.4 Addition Across Two Molecules of a 1,3-Diene

47.1.6.3.4.1 Method 1: Hydrocarbonation Using Nitroalkane Anions

47.1.6.3.4.2 Method 2: Hydrocarbonation Using Stabilized Carbanions

47.1.6.3.4.3 Method 3: Hydrocarbonation Using Reductive Coupling to Imines and Alkenes

47.1.6.3.4.4 Method 4: Carbonation Using Alkyl Radicals

47.1.6.3.4.5 Method 5: Addition of Ammonia and Amines

47.1.6.3.4.6 Method 6: Addition of Alcohols, Phenols, or Carboxylic Acids

47.1.6.3.4.7 Method 7: Addition of Arenesulfinic Acids

47.1.6.4 Synthesis from 1,4-Dienes, 1,5-Dienes, or Higher Dienes

47.1.6.4.1 Method 1: Catalytic Hydrogenation

47.1.6.4.1.1 Variation 1: Hydrogenation Using Nickel Catalysts

47.1.6.4.1.2 Variation 2: Hydrogenation Using Palladium Catalysts

47.1.6.4.1.3 Variation 3: Hydrogenation Using Platinum Catalysts

47.1.6.4.1.4 Variation 4: Hydrogenation Using Other Metal Catalysts

47.1.6.4.2 Method 2: Reduction by Magnesium

47.1.6.4.3 Method 3: Reduction by Diimide

47.1.6.4.4 Method 4: Reduction by Sodium Hydrazide/Hydrazine

47.1.6.4.5 Method 5: Reduction by Nicotinamide Adenine Dinucleotide Model Dihydropyridines

47.1.7 Synthesis by Isomerization

M. Yus and F. Foubelo

47.1.7 Synthesis by Isomerization

47.1.7.1 Method 1: Rearrangement from Terminal to Internal Alkenes

47.1.7.1.1 Variation 1: Using Ruthenium Complexes

47.1.7.1.2 Variation 2: Using Rhodium Catalysts

47.1.7.1.3 Variation 3: Using Palladium Complexes

47.1.7.1.4 Variation 4: Using Diphenyl Disulfone

47.1.7.2 Method 2: Rearrangement from Internal to Terminal Alkenes

47.1.7.3 Method 3: Rearrangement of Z- and E-Alkenes

47.1.7.3.1 Variation 1: Conversion of an E-Alkene into a Z-Alkene

47.1.7.3.2 Variation 2: Conversion of a Z-Alkene into an E-Alkene

47.1.7.4 Method 4: Allylic Rearrangement

47.1.7.4.1 Variation 1: Of Alcohols and Ethers

47.1.7.4.2 Variation 2: Of Esters and Imidates

47.1.7.4.3 Variation 3: Of Sulfoxides, Selenoxides, Sulfones, and Related Compounds

47.1.7.4.4 Variation 4: Of Azides

47.1.7.5 Method 5: Rearrangement of Vinylcyclopropanes

47.1.7.5.1 Variation 1: Under Thermal Conditions

47.1.7.5.2 Variation 2: Under Photochemical Conditions

47.1.7.5.3 Variation 3: Under Transition-Metal Catalysis

47.1.8 Synthesis from Other Alkenes without Isomerization

M. Yus and F. Foubelo

47.1.8 Synthesis from Other Alkenes without Isomerization

47.1.8.1 Method 1: Electrophilic Substitution

47.1.8.1.1 Variation 1: Acylation Reactions

47.1.8.1.2 Variation 2: Reactions of Vinylsilanes and Vinylstannanes

47.1.8.2 Method 2: Nucleophilic Substitution

47.1.8.2.1 Variation 1: Reactions with Carbon Nucleophiles

47.1.8.2.2 Variation 2: Reactions with Heteroatom Nucleophiles

47.1.8.3 Method 3: Alkylation of Organometallic Compounds

47.1.8.3.1 Variation 1: Reactions of Organolithium Compounds

47.1.8.3.2 Variation 2: Reactions of Organomagnesium Compounds

47.1.8.3.3 Variation 3: Reactions of Organocopper Compounds

47.2 Product Class 2: Cyclopropenes

M. S. Baird

47.2 Product Class 2: Cyclopropenes

47.2.1 Synthesis of Product Class 2

47.2.1.1 Method 1: Synthesis by Ring Closure with Formation of Two C—C Bonds

47.2.1.2 Method 2: Synthesis by Ring Closure with Formation of One C—C Bond

47.2.1.2.1 Variation 1: Dehydrohalogenation of Allylic Halides

47.2.1.2.2 Variation 2: Cyclizing Insertions of Methylenecarbenes (Vinylidenes) or Related Species

47.2.1.2.3 Variation 3: 1,3-Elimination from Propenes

47.2.1.2.4 Variation 4: By Formation of the C=C Bond

47.2.1.3 Method 3: Synthesis by Ring Contraction

47.2.1.4 Method 4: Synthesis by 1,2-Elimination

47.2.1.4.1 Variation 1: Dehydrohalogenation

47.2.1.4.2 Variation 2: Dehalogenation

47.2.1.4.3 Variation 3: Dehalosilylation

47.2.1.4.4 Variation 4: Dehydroxysilylation

47.2.1.5 Method 5: Synthesis by Rearrangement of Methylenecyclopropanes

47.2.1.6 Method 6: Synthesis from Other Cyclopropenes

47.2.1.6.1 Variation 1: By Alkylation of a Carbon Nucleophile

47.2.1.6.2 Variation 2: By Alkylation with an Electrophilic Reagent

47.2.1.6.3 Variation 3: By Ene Reactions

47.2.1.7 Method 7: Miscellaneous Methods

47.3 Product Class 3: Nonconjugated Di-, Tri-, and Oligoenes

K.-M. Roy

47.3 Product Class 3: Nonconjugated Di-, Tri-, and Oligoenes

47.3.1 Synthesis of Product Class 3

47.3.1.1 Synthesis with C—C Bond Formation

47.3.1.1.1 Method 1: Wittig-Type Reactions

47.3.1.1.2 Method 2: Coupling Reactions with Organometallic Compounds

47.3.1.1.2.1 Variation 1: With Organomagnesium Compounds

47.3.1.1.2.2 Variation 2: With Organoboron Compounds

47.3.1.1.2.3 Variation 3: With Organoaluminum and Organoindium Compounds

47.3.1.1.2.4 Variation 4: With Organosilicon and Organotin Compounds

47.3.1.1.2.5 Variation 5: With Other Organometallic Compounds

47.3.1.1.3 Method 3: Dimerization and Oligomerization Reactions

47.3.1.2 Synthesis by Elimination

47.3.1.2.1 Method 1: Synthesis from Cyclopropylcarbinols

47.3.1.2.2 Method 2: Synthesis from Iodohydrin Derivatives

47.3.1.2.3 Method 3: Hydroboration–Elimination of Enamines

47.3.1.3 Synthesis by Reduction

47.3.1.3.1 Method 1: Catalytic Hydrogenation

47.3.1.3.2 Method 2: Chemical Reduction

47.3.1.3.3 Method 3: Electrochemical Reduction

Keyword Index

Author Index

Abbreviations