Science of Synthesis: Cross Coupling and Heck-Type Reactions Vol. 3 E-Book

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

Beschreibung

In Science of Synthesis: Cross Coupling and Heck-Type Reactions, expert authors present and discuss the best and most reliable methods currently available for the formation of new carbon-carbon and carbon-heteroatom bonds using these reactions, highlighted with representative experimental procedures. Together, the three volumes of Cross Coupling and Heck-Type Reactions provide an extensive overview of the current state of the art in this field of central importance in modern chemistry, and are an invaluable resource for the practicing synthetic organic chemist.

This volume provides comprehensive coverage of the different classes of Heck-type reactions. It describes the state-of-the-art developments in each area whilst critically evaluating the strengths and weaknesses of the different methods. In accordance with the growing demand for synthetic efficiency and practicality in organic synthesis, many of these newly developed Heck-type methods feature operationally convenient conditions, high catalytic efficiency, and high levels of chemical, regiochemical, and stereochemical control. Metal-catalyzed C-H functionalization has also been developed into a powerful tool for organic synthesis, providing for original C-C disconnections in retrosynthetic analysis and improving the overall efficiency of the desired transformations. This volume also summarizes the most important concepts and methods in this hot research area.

This volume is part of a 3-volume set:

Cross Coupling and Heck-Type Reactions Workbench Edition

General information about Science of Synthesis

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 the pace and breadth of research intensifies, organic synthesis is playing an increasingly central role in the discovery process within all imaginable areas of science: from pharmaceuticals, agrochemicals, and materials science to areas of biology and physics, the most impactful investigations are becoming more and more molecular. As an enabling science, synthetic organic chemistry is uniquely poised to provide access to compounds with exciting and valuable new properties. Organic molecules of extreme complexity can, given expert knowledge, be prepared with exquisite efficiency and selectivity, allowing virtually any phenomenon to be probed at levels never before imagined. With ready access to materials of remarkable structural diversity, critical studies can be conducted that reveal the intimate workings of chemical, biological, or physical processes with stunning detail.

The sheer variety of chemical structural space required for these investigations and the design elements necessary to assemble molecular targets of increasing intricacy place extraordinary demands on the individual synthetic methods used. They must be robust and provide reliably high yields on both small and large scales, have broad applicability, and exhibit high selectivity. Increasingly, synthetic approaches to organic molecules must take into account environmental sustainability. Thus, atom economy and the overall environmental impact of the transformations are taking on increased importance.

The need to provide a dependable source of information on evaluated synthetic methods in organic chemistry embracing these characteristics was first acknowledged over 100 years ago, when the highly regarded reference source Houben–Weyl Methoden der Organischen Chemie was first introduced. Recognizing the necessity to provide a modernized, comprehensive, and critical assessment of synthetic organic chemistry, in 2000 Thieme launched Science of Synthesis, Houben–Weyl Methods of Molecular Transformations. This effort, assembled by almost 1000 leading experts from both industry and academia, provides a balanced and critical analysis of the entire literature from the early 1800s until the year of publication. The accompanying online version of Science of Synthesis provides text, structure, substructure, and reaction searching capabilities by a powerful, yet easy-to-use, intuitive interface.

From 2010 onward, Science of Synthesis is being updated quarterly with high-quality content via Science of Synthesis Knowledge Updates. The goal of the Science of Synthesis Knowledge Updates is to provide a continuous review of the field of synthetic organic chemistry, with an eye toward evaluating and analyzing significant new developments in synthetic methods. A list of stringent criteria for inclusion of each synthetic transformation ensures that only the best and most reliable synthetic methods are incorporated. These efforts guarantee that Science of Synthesis will continue to be the most up-to-date electronic database available for the documentation of validated synthetic methods.

Also from 2010, Science of Synthesis includes the Science of Synthesis Reference Library, comprising volumes covering special topics of organic chemistry in a modular fashion, with six main classifications: (1) Classical, (2) Advances, (3) Transformations, (4) Applications, (5) Structures, and (6) Techniques. Titles will include Stereoselective Synthesis, Water in Organic Synthesis, and Asymmetric Organocatalysis, among others. With expertevaluated content focusing on subjects of particular current interest, the Science of Synthesis Reference Library complements the Science of Synthesis Knowledge Updates, to make Science of Synthesis the complete information source for the modern synthetic chemist.

The overarching goal of the Science of Synthesis Editorial Board is to make the suite of Science of Synthesis resources the first and foremost focal point for critically evaluated information on chemical transformations for those individuals involved in the design and construction of organic molecules.

Throughout the years, the chemical community has benefited tremendously from the outstanding contribution of hundreds of highly dedicated expert authors who have devoted their energies and intellectual capital to these projects. We thank all of these individuals for the heroic efforts they have made throughout the entire publication process to make Science of Synthesis a reference work of the highest integrity and quality.

July 2010

The Editorial Board

E. M. Carreira (Zurich, Switzerland)

C. P. Decicco (Princeton, USA)

A. Fuerstner (Muelheim, Germany)

G. A. Molander (Philadelphia, USA)

P. J. Reider (Princeton, USA)

E. Schaumann (Clausthal-Zellerfeld, Germany)

M. Shibasaki (Tokyo, Japan)

E. J. Thomas (Manchester, UK)

B. M. Trost (Stanford, USA)

Volume Editor’s Preface

I am delighted to present this new volume in the Science of Synthesis Reference Library series addressing metal-catalyzed Heck-type reactions and C—C cross coupling via C—H activation. The formation of C—C bonds is of paramount importance in organic synthesis and has captured the attention of organic chemists since the very beginning of modern synthetic chemistry. Transition-metal-catalyzed coupling, and especially palladium-catalyzed coupling, has emerged as an efficient and selective method for the arylation and vinylation of a range of different substrates. Amongst the palladium-catalyzed couplings, the Heck reaction (or the Mizoroki–Heck reaction) is one of the most prominent examples. This was recently recognized by the Royal Swedish Academy of Sciences, who jointly awarded Richard F. Heck, Ei-ichi Negishi, and Akira Suzuki the 2010 Nobel Prize in Chemistry.

This volume provides comprehensive coverage of the different classes of Heck-type reactions. It describes the latest state-of-the-art developments in each area whilst critically evaluating the strengths and weaknesses of the different methods. In accordance with the growing demand for synthetic efficiency and practicality in organic synthesis, many of these newly developed Heck-type methods feature operationally convenient conditions, high catalytic efficiency, and high levels of chemical, regiochemical, and stereo-chemical control. Metal-catalyzed C—H functionalization has also been developed into a powerful tool for organic synthesis, providing for original C—C disconnections in retro-synthetic analysis and improving the overall efficiency of the desired transformations. This volume also summarizes the most important concepts and methods in this hot research area.

The different chapters have, in all cases, been authored by respected researchers active in the field. Of interest to both academic and industrial chemists, the introductory overview on each class of transformation is followed by presentation of the most important methods that have been developed, including experimental procedures. It is with satisfaction that I have observed the increased use of, and interest in, metal-catalyzed Heck-type reactions and C—H couplings over the last decade. I hope that this volume will appeal not only to experts in homogeneous catalysis but also to a broader group of organic and medicinal chemists, both in universities and in the pharmaceutical and related industries. I believe that this volume reflects the relevance and timeliness of the subject matter and will enhance current efforts to expand the scope and application of these powerful transformations.

I would like to take this opportunity to express my sincere gratitude to all the authors of this volume and thank them for their careful and comprehensive work. Furthermore, I would like to thank Associate Editor Dr Luke R. Odell, not only for his skilled efforts and concise work during the difficult process of editing and proofing the complete volume, but also for his highly valuable help to all of us who write in English but not as our first language. I also wish to express my appreciation to the outstanding staff at Thieme, in particular Dr. M. Fiona Shortt de Hernandez, Dr. Matthew Weston, and Ms. Michaela Frey, for their highly valuable help in preparing yet another timely volume in the Science of Synthesis Reference Library series.

M. Larhed (Uppsala, Sweden)

October, 2012

Cross Coupling and Heck-Type Reactions Volumes

Cross Coupling and Heck-Type Reactions 1

C—C Cross Coupling Using Organometallic PartnersVolume Editor: G. A. Molander

Cross Coupling and Heck-Type Reactions 2

Carbon—Heteroatom Cross Coupling and C—C Cross Coupling of Acidic C—H NucleophilesVolume Editor: J. P. Wolfe

Cross Coupling and Heck-Type Reactions 3

Metal-Catalyzed Heck-Type Reactions and C—C Cross Coupling via C—H ActivationVolume Editor: M. Larhed

Abstracts

3.1.1.1.1 Reaction with Aryl or Hetaryl Halides or Pseudohalides

C.-M. Andersson and M. Andersson

The arylation of terminal alkenes bearing mesomerically electron-withdrawing groups is the archetypal palladium(0)-catalyzed Heck reaction, also known as the Mizoroki–Heck reaction. These substrates generally provide a very high regioselectivity, with both steric and electronic factors favoring arylation at the terminal position of the alkene. Additionally, diastereoselectivity is generally very high, and products with an E configuration are obtained exclusively in most cases. In the wake of the pioneering studies on this reaction in which stoichiometric amounts of palladium reagents were used, iodoarenes were introduced as arylating agents in a catalytic version of the reaction; these were later supplemented by bromo- and chloroarenes. Subsequently, many other arylating agents, such as pseudohalides, aroyl chlorides, and diazonium or iodonium salts, have been introduced as electrophiles in the Mizoroki–Heck reaction. Later advances include the development of oxidative Heck arylations catalyzed by palladium(II) species.

This chapter aims to provide a general perspective on the applicability of this type of coupling chemistry, and to describe the depth and breadth of various aspects that have been researched and refined in making the Heck reaction of alkenes bearing electron-withdrawing groups a cornerstone of the art of C—C bond formation.

Keywords: arylation • electron-poor alkenes • catalysis • palladium • Heck reaction • Mizoroki–Heck reaction • alkenylation • aryl halides • oxidative arylation • arylboronic acids • iodonium salts • diazonium salts • aryl trifluoromethanesulfonates • ionic liquids

3.1.1.1.2 Reaction with (Het)Arylmetals or (Het)Arenes

E. W. Werner and M. S. Sigman

The intermolecular Heck reaction, in which a vinylic C—H bond is replaced by a C—C bond under palladium catalysis, is an indispensible tool for synthetic organic chemists. The reasons for this reliance include predictable regioselectivity in the formation of the new C—C bond when electronically biased alkenes are used, and the dependable delivery of configurationally pure E-alkene products. When palladium(II) salts are employed as catalysts in conjunction with organometallic reagents, an external oxidant is required to render the reaction catalytic. This strategy enables the reaction to perform well under mild conditions as compared to the elevated temperatures typically required when using palladium(0) catalysts. A critical review of the reagents and conditions capable of performing such transformations upon electron-deficient alkene substrates is presented.

Keywords: acrylates • arenes • arylation • arylmetals • electron-deficient alkenes • hetarenes • hetarylmetals • oxidative coupling • palladium(II) catalysis • styrenes

3.1.1.1.3 Reaction with Arene- or Hetarenecarboxylic Acids or Derivatives, or Related Compounds

M. Zhang and W. Su

This chapter presents the synthesis of aryl-substituted alkenes via transition-metal-catalyzed decarbonylative, decarboxylative, or desulfinylative Mizoroki–Heck cross-coupling reactions.

Keywords: alkenes • arylation • cross-coupling reactions • decarbonylation • decarboxylation • desulfinylation • Heck reaction • palladium catalysis • rhodium catalysis • transition-metal catalysis

3.1.1.1.4 Reaction with Nonaromatic Halides or Sulfonates, or Related Compounds

M. Weimar and M. J. Fuchter

The Heck reaction is a widely used method in organic synthesis. This report concerns the development of methodologies to apply Heck-type chemistry to electron-poor alkenes with one or more electron-withdrawing groups and alkenyl and other nonaromatic electrophiles.

Keywords: acrylates • alkenes • alkenylation • benzylation • catalysts • C=C bonds • C—C coupling • cross-coupling reactions • dienes • enols • Heck reaction • iodonium compounds • oxidative addition • palladium catalysts • palladium complexes • phosphates • styrenes • sulfonates • vinyl compounds

3.1.1.2 Alkenes with Allylic Substitution and Homologues as Reaction Components

J. Le Bras and J. Muzart

The intermolecular coupling of aryl or vinyl halides (or pseudohalides) with linear alkenes having an allylic or homoallylic heteroatomic substituent occurs under palladium-catalyzed conditions. The 1,2-insertion of the aryl- or vinylpalladium intermediate into the double bond is followed by the elimination of either a hydride or the heteroatomic substituent. This chapter focuses on selective procedures.

Keywords: arylation • vinylation • catalysis • regioselectivity • palladium • β-hydride elimination • β-heteroatom elimination • carbon—heteroatom cleavage • isomerization

3.1.1.3.1 Reaction with Aryl or Hetaryl Halides or Pseudohalides

S. Liu and J. Xiao

This chapter describes the palladium-catalyzed Heck reaction of electron-rich alkenes with aryl, hetaryl, or vinyl halides or pseudohalides. The alkenes covered include vinyl ethers, enamides, and enamines generated in situ from aldehydes. The electron-neutral styrenes are also mentioned. Depending on the arylating or vinylating reagent, ligand, additive, and solvent used, the reaction can take place at either the α or β position of the alkene, and, in the past two decades or so, significant progress has been made allowing precise control of the regioselectivity.

Keywords: Heck reaction • regioselectivity • electron-rich alkenes • vinyl ethers • enamides • enamines • styrenes

3.1.1.3.2 Reaction with Arylboronic Acids or Derivatives or Aroyl Halides

J. Lindh and M. Larhed

The use of electron-rich alkenes in Heck reactions was originally associated with poor regiocontrol, resulting in unwanted mixtures of regioisomers, thus severely hampering the utility of electron-rich alkenes. Today, excellent regiocontrol can be obtained by employing suitable reaction conditions. The use of electron-rich alkenes, such as enamides and vinyl ethers, in coupling reactions with arylboron compounds under cationic conditions provides easy access to the corresponding aryl ketones. Additionally, vinyl acetate can function as a convenient ethene precursor to form styrenes in coupling reactions with arylboron compounds.

Keywords: arylation • enamides • vinyl ethers • vinyl acetate • boronic acids • trifluoroborates • aroyl chlorides • styrene • acetophenone • oxidative Heck reaction • catalysis • regioselectivity • palladium

3.1.1.3.3 Reaction with Nonaromatic Alkenyl Halides or Alkenyl Sulfonates

P. Nilsson

Keywords: vinylation • catalysis • regioselectivity • palladium • dienes • enol ethers • enamides

3.1.1.4 Cyclic Alkenes as Reaction Components

V. Coeffard and P. J. Guiry

This chapter collates the relevant literature on intermolecular Mizoroki–Heck reactions of cyclic alkenes leading to the enantioselective and non-enantioselective construction of functionalized alicyclic compounds or heterocycles.

Keywords: Heck reaction • cycloalkenes • C—C coupling • palladium • regioselectivity • diastereoselectivity • enantioselectivity • oxygen and nitrogen heterocycles • chiral ligand • phosphines • dihydrooxazole ligands

3.1.1.5 Alkenes with Metal-Directing Groups as Reaction Components

A. Trejos and L. R. Odell

The use of electron-rich alkenes in Heck reactions was originally associated with poor regiocontrol, resulting in unwanted mixtures of regioisomers, thus severely hampering the utility of electron-rich alkenes. Chelation control has arisen as an attractive strategy to dictate the product outcome, as the directing effect of these substrates and the favorable formation of five- or six-membered chelates result in excellent regioselectivities. Today, excellent regiocontrol can be obtained by employing alkenes containing suitable catalyst-presenting groups. In addition, high levels of stereocontrol can also be obtained by using appropriate chiral catalyst presenting groups.

Keywords: arylation • chelation • catalysis • regioselectivity • palladium • stereoselectivity • vinyl ethers • C—H activation

3.1.2.1 Formation of Carbocycles

K. Geoghegan and P. Evans

The intramolecular Mizoroki–Heck reaction is an important method for the formation of cyclic molecules, which would often be nontrivial to assemble by alternative means. Coupling between an sp2-hybridized carbon atom and an alkene generates a C—C bond which is included within a newly formed ring. In the absence of an additional coupled process, a new alkene is also generated. A variety of ring sizes may be accessed in this class of reaction and in many instances the adducts may be isolated in excellent chemical yield. The process is typically effected under the influence of palladium catalysis and the many published examples indicate that a variety of functionalities may be tolerated without interference. Within this chapter, examples have been selected from the recent literature to illustrate the utility of this method for the construction of carbocyclic compounds.

Keywords: intramolecular • Mizoroki–Heck reaction • cyclization • palladium • catalysis

3.1.2.2 Formation of Heterocycles

S. G. Stewart

The formation of heterocycles through the Heck cross-coupling reaction has been studied extensively as it allows potential efficient access to a large variety of compounds. High-yielding production of heterocyclic frameworks is of paramount importance in natural product based research as well as in medicinal chemistry programs. In particular, the intramolecular Heck reaction has been used extensively for this purpose. Cyclization methods producing the five-membered pyrrole ring contained within the indole ring system are by far the most common, possibly due to the plethora of such compounds found in nature and their corresponding biological activity. In most examples discussed in this chapter, the mechanism by which the intramolecular Heck cross coupling operates is through the standard oxidative addition, migratory insertion, C—C bond rotation, syn-β-hydride elimination, and reductive elimination pathway. However, sometimes this “standard” Mizoroki–Heck catalytic cycle is not always followed, and rare examples such as anti-elimination or oxidative Heck reaction (intramolecular Fujiwara–Moritani reaction) are further emphasized when they arise.

Keywords: Heck reaction • palladium • catalysis • intramolecular • heterocycles • cyclization

3.1.2.3 Stereoselective Formation of Tertiary and Quaternary Centers

G. Broggini, E. Borsini, and U. Piarulli

The intramolecular Heck (or Mizoroki–Heck) reaction represents a well-established methodology for the construction of isolated, fused, bridged, or spiroannulated rings of various sizes. Its asymmetric version has become a powerful tool for the synthesis of both tertiary and quaternary stereocenters. Within this chapter, intramolecular asymmetric Heck reactions are discussed in sections according to the following subdivision: (i) the substitution level of the stereocenter that is formed, i.e. the formation of tertiary stereocenters (by reaction of monosubstituted alkenyl carbon atoms) or quaternary stereocenters (by reaction of disubstituted alkenyl carbon atoms); (ii) the structure of the alkenyl substrate, i.e. acyclic or cyclic alkenes, leading to fused bi- or polycyclic products; (iii) the nature of the aryl or vinyl reagents, i.e. iodides, bromides, or trifluoromethanesulfonates; and (iv) reaction of prochiral substrates in the presence of chiral ligands, or control of the configuration of the newly formed stereocenter by existing elements of stereogenicity (use of chiral substrates).

Keywords: homogeneous catalysis • asymmetric synthesis • Heck reaction • palladium • enantioselectivity • diastereoselectivity • cyclization • chiral ligands • intramolecular reactions • desymmetrization • spiro compounds • polycycles

3.2.1 Intermolecular Coupling via C(sp2)—H Activation

A. Kantak and B. DeBoef

The synthesis of biaryl C—C bonds via the arylation of the C—H bonds of either simple arenes or heteroarenes is a rapidly expanding field. In particular, palladium, rhodium, ruthenium, iron, and copper catalysts can be used to couple a C—H carbon of one arene with a carbon bearing a reactive moiety such as a halogen, pseudohalogen, borane, or silane. Due to the ubiquity of C—H bonds in organic molecules, it is tempting to assume that these reactions will be plagued by the formation of multiple regioisomers; however, it has been repeatedly demonstrated that specific C—H bonds can be functionalized. The regioselectivity is often governed by the substrate, catalyst, or reaction conditions. This chapter describes the current state of the art in this field and guides the reader in choosing the appropriate reaction conditions for forming biaryl C—C bonds via C—H arylation. Particular focus is placed on substrates containing directing groups to achieve regioselectivity and on heteroaromatic substrates.

Keywords: arylation • hetarenes • C—H activation • catalysis • biaryls

3.2.2 Intramolecular Coupling via C(sp2)—H Activation

E. Suna and K. Shubin

This chapter focuses on transition-metal-catalyzed intramolecular C—H activation/C—C bond formation with a remote tethered carbon atom. All of the reviewed examples feature the in situ transformation of the aryl or hetaryl C—H bond into a reactive carbon—metal bond. Palladium, rhodium, iridium, and ruthenium species are used as catalysts. Several classes of cyclization reactions are covered, including addition to multiple bonds (alkenes, alkynes, and ketones) and cross coupling with (pseudo)halides.

Keywords: palladium • rhodium • ruthenium • iridium • C—H activation • cross coupling • addition • cyclization • Fujiwara–Moritani • hydroarylation • intramolecular • enantioselective

3.2.3 Coupling via C(sp3)—H Activation under Palladium Catalysis

D. Kalyani and L. V. Desai

This chapter describes the synthetic and mechanistic aspects of palladium-catalyzed arylation, carbonylation, alkenylation, and alkylation of C(sp3)—H bonds. Recent accomplishments in the enantioselective construction of C(sp3)—C bonds via C(sp3)—H activation are also detailed. Additionally, the few reported examples of the strategic application of these powerful C(sp3)—C bond forming transformations toward complex molecule synthesis are presented.

Keywords: palladium • C(sp3)–H activation • C—C bonds • asymmetric catalysis • arylation • alkenylation • carbonylation • alkylation

3.3 C—C Cross Coupling via Double C—H Activation

C. S. Yeung, N. Borduas, and V. M. Dong

Palladium catalysts promote oxidative C—C bond formation between two arene coupling partners by twofold C—H activation. The observed regioselectivity for the biaryl products is predictable based on proximity to Lewis base functionality and inherent electronic bias.

Keywords: arylation • C—C bond formation • C—H bond activation • cross-coupling reactions • dehydrogenation • oxidation • palladium catalysis

Cross Coupling and Heck-Type Reactions 3 Metal-Catalyzed Heck-Type Reactions and C—C Cross Coupling via C—H Activation

Preface

Volume Editor’s Preface

Abstracts

Table of Contents

Introduction

L. R. Odell and M. Larhed

3.1 Heck Reactions

3.1.1 Intermolecular Reactions

3.1.1.1 Electron-Poor Alkenes as Reaction Components

3.1.1.1.1 Reaction with Aryl or Hetaryl Halides or Pseudohalides

C.-M. Andersson and M. Andersson

3.1.1.1.2 Reaction with (Het)Arylmetals or (Het)Arenes

E. W. Werner and M. S. Sigman

3.1.1.1.3 Reaction with Arene- or Hetarenecarboxylic Acids or Derivatives, or Related Compounds

M. Zhang and W. Su

3.1.1.1.4 Reaction with Nonaromatic Halides, Sulfonates, or Related Compounds

M. Weimar and M.J. Fuchter

3.1.1.2 Alkenes with Allylic Substitution and Homologues as Reaction Components

J. Le Bras and J. Muzart

3.1.1.3 Electron-Rich Alkenes as Reaction Components

3.1.1.3.1 Reaction with Aryl or Hetaryl Halides or Pseudohalides

S. Liu and J. Xiao

3.1.1.3.2 Reaction with Arylboronic Acids or Derivatives or Aroyl Halides

J. Lindh and M. Larhed

3.1.1.3.3 Reaction with Nonaromatic Alkenyl Halides or Alkenyl Sulfonates

P. Nilsson

3.1.1.4 Cyclic Alkenes as Reaction Components

V. Coeffard and P. J. Guiry

3.1.1.5 Alkenes with Metal-Directing Groups as Reaction Components

A. Trejos and L. R. Odell

3.1.2 Intramolecular Reactions

3.1.2.1 Formation of Carbocycles

K. Geoghegan and P. Evans

3.1.2.2 Formation of Heterocycles

S. G. Stewart

3.1.2.3 Stereoselective Formation of Tertiary and Quaternary Centers

G. Broggini, E. Borsini, and U. Piarulli

3.2 C–C Cross Coupling via Single C–H Activation

3.2.1 Intermolecular Coupling via C(sp2)–H Activation

A. Kantak and B. DeBoef

3.2.2 Intramolecular Coupling via C(sp2)–H Activation

E. Suna and K. Shubin

3.2.3 Coupling via C(sp3)–H Activation under Palladium Catalysis

D. Kalyani and L. V. Desai

3.3 C–C Cross Coupling via Double C–H Activation

C. S. Yeung, N.Borduas, and V.M.Dong

Keyword Index

Author Index

Abbreviations

Table of Contents

Introduction

L. R. Odell and M. Larhed

Introduction

3.1 Heck Reactions

3.1.1 Intermolecular Reactions

3.1.1.1 Electron-Poor Alkenes as Reaction Components

3.1.1.1.1 Reaction with Aryl or Hetaryl Halides or Pseudohalides

C.-M. Andersson and M. Andersson

3.1.1.1.1 Reaction with Aryl or Hetaryl Halides or Pseudohalides

3.1.1.1.1.1 Arylation of Alkenes Carrying at Least One Keto, Ester, Nitrile, or Amide Group

3.1.1.1.1.1.1 Arylations with Aryl Halides

3.1.1.1.1.1.1.1 With Iodoarenes or Bromoarenes

3.1.1.1.1.1.1.1.1 With Resin-Bound Aryl Halides

3.1.1.1.1.1.1.1.2 Arylations in Ionic Liquids

3.1.1.1.1.1.1.1.3 Continuous-Flow Heck Arylation

3.1.1.1.1.1.1.1.4 Substrates Carrying More than One Keto, Ester, Nitrile, or Amide Group

3.1.1.1.1.1.1.2 With Chloroarenes

3.1.1.1.1.1.2 Hetarylations with Hetaryl Halides

3.1.1.1.1.1.3 Arylations with Other Electrophiles

3.1.1.1.1.1.3.1 With Diazonium Salts

3.1.1.1.1.1.3.2 With Iodonium Salts

3.1.1.1.1.1.3.3 With Aryl Trifluoromethanesulfonates

3.1.1.1.1.2 Arylation of Alkenes Carrying at Least One Sulfoxide, Sulfone, Sulfonate, or Sulfinate Group

3.1.1.1.1.2.1 Arylations with Aryl Halides

3.1.1.1.1.2.2 Arylations with Arenediazonium Salts

3.1.1.1.1.3 Arylation of Alkenes Carrying at Least One Phosphonic, Phosphinic, Nitro, or Nitroso Group

3.1.1.1.1.3.1 Arylations with Aryl Halides

3.1.1.1.1.3.2 Arylations with Arenediazonium Salts

3.1.1.1.1.4 Arylation of Alkenes Carrying at Least One Halomethyl Group

3.1.1.1.1.5 Arylation of Alkenes Carrying at Least One Aryl Group

3.1.1.1.1.5.1 Arylations with Aryl Halides

3.1.1.1.1.5.2 Arylations with Other Arylating Agents

3.1.1.1.1.6 Arylation of Alkenes Carrying at Least One Hetaryl Group

3.1.1.1.1.6.1 Hetarylations with Hetaryl Halides

3.1.1.1.2 Reaction with (Het)Arylmetals or (Het)Arenes

E. W. Werner and M. S. Sigman

3.1.1.1.2 Reaction with (Het)Arylmetals or(Het)Arenes

3.1.1.1.2.1 Reaction with (Het)Arylmetals

3.1.1.1.2.1.1 Reaction with Arylmercury Reagents

3.1.1.1.2.1.2 Reaction with Arylstannane Reagents

3.1.1.1.2.1.3 Reaction with Arylsilane Reagents

3.1.1.1.2.1.4 Reaction with Arylboronic Acids and Derivatives

3.1.1.1.2.1.5 Reaction with Other Electrophilic Reagents

3.1.1.1.2.2 Reaction with (Het)Arenes

3.1.1.1.2.2.1 Reaction with Benzene or Electron-Rich (Het)Arenes

3.1.1.1.2.2.2 Reaction with Electron-Deficient (Het)Arenes

3.1.1.1.2.3 Non-Palladium-Catalyzed Reactions

3.1.1.1.3 Reaction with Arene- or Hetarenecarboxylic Acids or Derivatives, or Related Compounds

M. Zhang and W. Su

3.1.1.1.3 Reaction with Arene- or Hetarenecarboxylic Acids or Derivatives, or Related Compounds

3.1.1.1.3.1 Decarbonylative Reactions of Arenecarboxylic Acid Derivatives

3.1.1.1.3.1.1 Reaction with Aroyl Chlorides

3.1.1.1.3.1.2 Reaction with Arenecarboxylic Anhydrides

3.1.1.1.3.1.3 Reaction with Arenecarboxylates

3.1.1.1.3.2 Decarboxylative Reactions of Arenecarboxylic Acids

3.1.1.1.3.2.1 Reaction Using Palladium Catalysis

3.1.1.1.3.2.2 Reaction Using Rhodium Catalysis

3.1.1.1.3.3 Miscellaneous Reactions

3.1.1.1.3.3.1 Reaction with Arenesulfonyl Chlorides

3.1.1.1.3.3.2 Reaction with Arenesulfinic Acids

3.1.1.1.3.3.3 Reaction with Arylphosphonic Acids

3.1.1.1.4 Reaction with Nonaromatic Halides, Sulfonates, or Related Compounds

M. Weimar and M. J. Fuchter

3.1.1.1.4 Reaction with Nonaromatic Halides, Sulfonates, or Related Compounds

3.1.1.1.4.1 Reaction with Alkenyl–X Electrophiles

3.1.1.1.4.1.1 Reaction with Alkenyl Iodides

3.1.1.1.4.1.2 Reaction with Alkenyl Bromides

3.1.1.1.4.1.3 Reaction with Alkenyl Chlorides

3.1.1.1.4.1.4 Reaction with Alkenyliodonium Salts

3.1.1.1.4.1.5 Reaction with Alkenyl 4-Toluenesulfonates

3.1.1.1.4.1.6 Reaction with Alkenyl Trifluoromethanesulfonates and Nonafluorobutanesulfonates

3.1.1.1.4.1.7 Reaction with Alkenyl Phosphates

3.1.1.1.4.1.8 Reaction with Alkenylboronates

3.1.1.1.4.2 Reaction with Benzyl–X Electrophiles

3.1.1.1.4.2.1 Reaction with Benzyl Chlorides

3.1.1.1.4.2.2 Reaction with Benzyl Trifluoroacetates

3.1.1.1.4.3 Reaction with Allyl–X Electrophiles

3.1.1.1.4.3.1 Reaction with Allyl 4-Toluenesulfonates

3.1.1.1.4.4 Reaction with Other Nonaromatic Electrophiles

3.1.1.2 Alkenes with Allylic Substitution and Homologues as Reaction Components

J. Le Bras and J. Muzart

3.1.1.2 Alkeneswith Allylic Substitution and Homologues as Reaction Components

3.1.1.2.1 Couplings with Retention of an Allylic or Homoallylic Substituent

3.1.1.2.1.1 Using Allylic or Homoallylic Alcohols