Organic Reactions, Volume 116 E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Serie: Organic Reactions
• Sprache: Englisch

Seitenzahl: 456

Veröffentlichungsjahr: 2024

Beschreibung

A carefully curated review of the scientific literature, Volume 116 of Organic Reactions presents critical discussions of widely used organic reactions or particular steps of a reaction. The material is treated from a preparative viewpoint, with emphasis on limitations, interfering influences, effects of structure and the selection of experimental techniques. The work includes tables that contain all possible examples of the reaction under consideration. Detailed procedures illustrate the significant modifications of each method.
Launched in 1942, the Organic Reactions series today is a leading secondary- and tertiary-level source for organic chemists across the world.

Leseprobe

Table of Contents

Cover

Table of Contents

Title Page

Copyright

INTRODUCTION TO THE SERIES BY ROGER ADAMS, 1942

INTRODUCTION TO THE SERIES BY SCOTT E. DENMARK, 2008

PREFACE TO VOLUME 116

1 A HALF CENTURY OF THE SONOGASHIRA REACTION

ACKNOWLEDGMENTS

INTRODUCTION

MECHANISM AND STEREOCHEMISTRY

SCOPE AND LIMITATIONS

APPLICATIONS TO SYNTHESIS

COMPARISON WITH OTHER METHODS

EXPERIMENTAL CONDITIONS

EXPERIMENTAL PROCEDURES

LIST OF ABBREVIATIONS

TABULAR SURVEY

1 A HALF CENTURY OF THE SONOGASHIRA REACTION

TABULAR SURVEY

REFERENCES

CUMULATIVE CHAPTER TITLES BY VOLUME

Volume 1 (1942)

Volume 2 (1944)

Volume 3 (1946)

Volume 4 (1948)

Volume 5 (1949)

Volume 6 (1951)

Volume 7 (1953)

Volume 8 (1954)

Volume 9 (1957)

Volume 10 (1959)

Volume 11 (1960)

Volume 12 (1962)

Volume 13 (1963)

Volume 14 (1965)

Volume 15 (1967)

Volume 16 (1968)

Volume 17 (1969)

Volume 18 (1970)

Volume 19 (1972)

Volume 20 (1973)

Volume 21 (1974)

Volume 22 (1975)

Volume 23 (1976)

Volume 24 (1976)

Volume 25 (1977)

Volume 26 (1979)

Volume 27 (1982)

Volume 28 (1982)

Volume 29 (1983)

Volume 30 (1984)

Volume 31 (1984)

Volume 32 (1984)

Volume 33 (1985)

Volume 34 (1985)

Volume 35 (1988)

Volume 36 (1988)

Volume 37 (1989)

Volume 38 (1990)

Volume 39 (1990)

Volume 40 (1991)

Volume 41 (1992)

Volume 42 (1992)

Volume 43 (1993)

Volume 44 (1993)

Volume 45 (1994)

Volume 46 (1994)

Volume 47 (1995)

Volume 48 (1995)

Volume 49 (1997)

Volume 50 (1997)

Volume 51 (1997)

Volume 52 (1998)

Volume 53 (1998)

Volume 54 (1999)

Volume 55 (1999)

Volume 56 (2000)

Volume 57 (2001)

Volume 58 (2001)

Volume 59 (2001)

Volume 60 (2002)

Volume 61 (2002)

Volume 62 (2003)

Volume 63 (2004)

Volume 64 (2004)

Volume 65 (2005)

Volume 66 (2005)

Volume 67 (2006)

Volume 68 (2007)

Volume 69 (2007)

Volume 70 (2008)

Volume 71 (2008)

Volume 72 (2008)

Volume 73 (2008)

Volume 74 (2009)

Volume 75 (2011)

Volume 76 (2012)

Volume 77 (2012)

Volume 78 (2012)

Volume 79 (2013)

Volume 80 (2013)

Volume 81 (2013)

Volume 82 (2013)

Volume 83 (2014)

Volume 84 (2014)

Volume 85 (2014)

Volume 86 (2015)

Volume 87 (2015)

Volume 88 (2015)

Volume 89 (2015)

Volume 90 (2016)

Volume 91 (2016)

Volume 92 (2016–2017)

Volume 93 (2017)

Volume 94 (2017)

Volume 95 (2018)

Volume 96 (2018)

Volume 97 (2019)

Volume 98 (2019)

Volume 99 (2019)

Volume 100 (2019)

Volume 101 (2020)

Volume 102 (2020)

Volume 103 (2020)

Volume 104 (2020)

Volume 105 (2021)

Volume 106 (2021)

Volume 107 (2021)

Volume 108 (2021)

Volume 109 (2022)

Volume 110 (2022)

Volume 111 (2022)

Volume 112 (2022)

Volume 113 (2023)

Volume 114 (2024)

Volume 115 (2024)

AUTHOR INDEX, VOLUMES 1–116

Index

End User License Agreement

List of Illustrations

Chapter 1a

Scheme 1

Scheme 2

Scheme 3

Scheme 4

Scheme 5

Scheme 6

Scheme 7

Scheme 8

Scheme 9

Scheme 10

Scheme 11

Scheme 12

Scheme 13

Scheme 14

Scheme 15

Scheme 16

Scheme 17

Scheme 18

Scheme 19

Scheme 20

Scheme 21

Scheme 22

Scheme 23

Scheme 24

Scheme 25

Scheme 26

Scheme 27

Scheme 28

Scheme 29

Scheme 30

Scheme 31

Scheme 32

Scheme 33

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Scheme 37

Scheme 38

Scheme 39

Scheme 40

Scheme 41

Scheme 42

Scheme 43

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Scheme 45

Scheme 46

Scheme 47

Scheme 48

Scheme 49

Figure 1 Alternative electrophilic partners for Pd‐catalyzed cross‐coupling ...

Scheme 50

Scheme 51

Scheme 52

Scheme 53

Scheme 54

Scheme 55

Scheme 56

Scheme 57

Figure 2 Heteroatom‐substituted alkyne partners for the Sonogashira reaction...

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Scheme 88

Figure 3 Examples of long‐chain polyacetylene alcohols from

Diplastrella

spo...

Scheme 89

Scheme 90

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Scheme 96

Scheme 97

Figure 4 Alkynylborane reagents used in Pd‐catalyzed cross‐coupling reaction...

Scheme 98

Scheme 99

Scheme 100

Scheme 101

Scheme 102

Scheme 103

Scheme 104

Scheme 105

Scheme 106

Scheme 107

Scheme 108

Guide

Cover

Table of Contents

Series Page

TITLE PAGE

COPYRIGHT

INTRODUCTION TO THE SERIES BY ROGER ADAMS, 1942

INTRODUCTION TO THE SERIES BY SCOTT E. DENMARK, 2008

PREFACE TO VOLUME 116

Begin Reading

AUTHOR INDEX, VOLUMES 1–116

Index

End User License Agreement

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FORMER MEMBERS OF THE BOARDOF EDITORS AND DIRECTORS

JEFFREY

AUBÉ

DAVID

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CHA

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CURRAN

SAMUEL

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HUW

M. L.

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SCOTT

E.

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VICTOR

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‐

HAGUE

STEPHEN

HANESSIAN

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A.

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, 

JR

.

THEODORE

L.

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COPE

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Y.

CURTIN

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G.

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FIESER

HEINZ

W.

GSCHWEND

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F.

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O.

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M.

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ANDREW

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WEINSTEIN

JAMES

D.

WHITE

Organic Reactions

VOLUME 116A

EDITORIAL BOARD

KEVIN H. SHAUGHNESSY, Editor‐in‐Chief

STEVEN M. WEINREB, Executive Editor

PAUL

R.

BLAKEMORE

BO

QU

ANDRE

CHARETTE

IAN

J.

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GRANGE

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D.

TOWNSEND

DENNIS

G.

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BEN

W. H.

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PIERCE

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ASSOCIATE EDITORS

STEPHANIE FRANKENBERGER

ALEXANDER SCHERER

KENKICHI SONOGRASHIRA

RIK R. TYKWINSKI

DOMINIK WENDINGER

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INTRODUCTION TO THE SERIES BY ROGER ADAMS, 1942

In the course of nearly every program of research in organic chemistry, the investigator finds it necessary to use several of the better‐known synthetic reactions. To discover the optimum conditions for the application of even the most familiar one to a compound not previously subjected to the reaction often requires an extensive search of the literature; even then a series of experiments may be necessary. When the results of the investigation are published, the synthesis, which may have required months of work, is usually described without comment. The background of knowledge and experience gained in the literature search and experimentation is thus lost to those who subsequently have occasion to apply the general method. The student of preparative organic chemistry faces similar difficulties. The textbooks and laboratory manuals furnish numerous examples of the application of various syntheses, but only rarely do they convey an accurate conception of the scope and usefulness of the processes.

For many years American organic chemists have discussed these problems. The plan of compiling critical discussions of the more important reactions thus was evolved. The volumes of Organic Reactions are collections of chapters each devoted to a single reaction, or a definite phase of a reaction, of wide applicability. The authors have had experience with the processes surveyed. The subjects are presented from the preparative viewpoint, and particular attention is given to limitations, interfering influences, effects of structure, and the selection of experimental techniques. Each chapter includes several detailed procedures illustrating the significant modifications of the method. Most of these procedures have been found satisfactory by the author or one of the editors, but unlike those in Organic Syntheses, they have not been subjected to careful testing in two or more laboratories. Each chapter contains tables that include all the examples of the reaction under consideration that the author has been able to find. It is inevitable, however, that in the search of the literature some examples will be missed, especially when the reaction is used as one step in an extended synthesis. Nevertheless, the investigator will be able to use the tables and their accompanying bibliographies in place of most or all of the literature search so often required. Because of the systematic arrangement of the material in the chapters and the entries in the tables, users of the books will be able to find information desired by reference to the table of contents of the appropriate chapter. In the interest of economy, the entries in the indices have been kept to a minimum, and, in particular, the compounds listed in the tables are not repeated in the indices.

The success of this publication, which will appear periodically, depends upon the cooperation of organic chemists and their willingness to devote time and effort to the preparation of the chapters. They have manifested their interest already by the almost unanimous acceptance of invitations to contribute to the work. The editors will welcome their continued interest and their suggestions for improvements in Organic Reactions.

INTRODUCTION TO THE SERIES BY SCOTT E. DENMARK, 2008

In the intervening years since “The Chief” wrote this introduction to the second of his publishing creations, much in the world of chemistry has changed. In particular, the last decade has witnessed a revolution in the generation, dissemination, and availability of the chemical literature with the advent of electronic publication and abstracting services. Although the exponential growth in the chemical literature was one of the motivations for the creation of Organic Reactions, Adams could never have anticipated the impact of electronic access to the literature. Yet, as often happens with visionary advances, the value of this critical resource is now even greater than at its inception.

From 1942 to the 1980's the challenge that Organic Reactions successfully addressed was the difficulty in compiling an authoritative summary of a preparatively useful organic reaction from the primary literature. Practitioners interested in executing such a reaction (or simply learning about the features, advantages, and limitations of this process) would have a valuable resource to guide their experimentation. As abstracting services, in particular Chemical Abstracts and later Beilstein, entered the electronic age, the challenge for the practitioner was no longer to locate all of the literature on the subject. However, Organic Reactions chapters are much more than a surfeit of primary references; they constitute a distillation of this avalanche of information into the knowledge needed to correctly implement a reaction. It is in this capacity, namely to provide focused, scholarly, and comprehensive overviews of a given transformation, that Organic Reactions takes on even greater significance for the practice of chemical experimentation in the 21st century.

Adams' description of the content of the intended chapters is still remarkably relevant today. The development of new chemical reactions over the past decades has greatly accelerated and has embraced more sophisticated reagents derived from elements representing all reaches of the Periodic Table. Accordingly, the successful implementation of these transformations requires more stringent adherence to important experimental details and conditions. The suitability of a given reaction for an unknown application is best judged from the informed vantage point provided by precedent and guidelines offered by a knowledgeable author.

As Adams clearly understood, the ultimate success of the enterprise depends on the willingness of organic chemists to devote their time and efforts to the preparation of chapters. The fact that, at the dawn of the 21st century, the series continues to thrive is fitting testimony to those chemists whose contributions serve as the foundation of this edifice. Chemists who are considering the preparation of a manuscript for submission to Organic Reactions are urged to contact the Editor‐in‐Chief.

PREFACE TO VOLUME 116

Their affinities being weaker, (the noble metals) do not present that variety of combinations, belonging to the more common metals, which renders them so extensively useful in the arts; nor are they, in consequence, so necessary and important in the operations of nature.

Michael Faraday

In lecturing about gold, silver, mercury, palladium, platinum, rhodium, iridium, and osmium in 1818, Faraday could not have envisioned the crucial role that these noble metals play in modern society. In particular, palladium is critical to modern chemistry and society. Palladium catalyzes a wide range of reaction types, including oxidation, hydrogenation, dehydrogenation, and carbon‐element bond formation. Large‐scale applications of palladium catalysts include catalytic converters, oil refining, and hydrogenation of vegetable oils. Heterogeneous palladium catalysts (e.g. Pd/C, Lindlar's catalyst) are widely used for hydrogenation of alkenes and alkynes. Over the past 50 years, palladium‐catalyzed cross‐coupling reactions have revolutionized the assembly of organic molecules by providing efficient routes to the formation of carbon–carbon and carbon–heteroatom bonds. The Heck, Suzuki‐Miyaura, Negishi, Stille, and Buchwald‐Hartwig reactions, for example, have become indispensable tools in the synthesis of natural products, pharmaceuticals, agricultural chemicals, and electronic materials.

This volume contains a single chapter by Stephanie Frankenberger, Dominik Wendinger, Alexander Scherer, Kenkichi Sonogashira, and Rik R. Tykwinski describing the development and application of the Sonogashira reaction. The Sonogashira reaction is the palladium‐ and copper‐catalyzed coupling of sp2‐hybridized carbon (pseudo)halides with terminal alkynes to afford conjugated alkyne products. Palladium‐catalyzed coupling of sp2‐hybridized carbon halides and terminal alkynes was independently reported in 1975 by Sonogashira, Heck, and Cassar. Sonogashira's key insight was the use of a copper(I) salt to catalyze the alkynylation of the palladium‐aryl intermediate. Sonogashira's conditions proceed under much milder conditions than the Heck and Cassar reactions. The mild conditions and broad generality of the Sonogashira reaction have resulted in it being the preferred method for the synthesis of conjugated alkynes, which are important intermediates in the synthesis of natural products, pharmaceuticals, and organic materials.

The Mechanism section outlines the key mechanistic features of the palladium‐ and copper‐catalyzed Sonogashira coupling. The key steps in the palladium catalytic cycle are oxidative addition of the organic electrophile, transmetalation of the acetylide anion from copper to palladium, and reductive elimination of the product. The copper cycle involves π‐coordination of the alkyne to copper, followed by deprotonation of the alkyne to form the copper(I)‐acetylide. Transmetalation of the acetylide to palladium closes the copper cycle. This section also describes possible mechanisms for the copper‐free variants of the Sonogashira reaction. The Scope and Limitations section covers both the organic electrophile and the alkyne coupling partner. The electrophile section is further subdivided into sections discussing aryl, heteroaryl, alkenyl halide or triflate electrophiles, as well as other miscellaneous classes of electrophiles. The alkyne section discusses the use of acetylene, substituted acetylenes, and polyynes.

The Applications to Synthesis section highlights the diverse applications of the Sonogashira reaction. Applications of the Sonogashira reaction to the synthesis of phthalocyanines and porphyrins, linear and cyclic conjugated materials, natural products, and pharmaceutical intermediates are demonstrated. The Comparison with Other Methods section discusses several homologation methods that convert an aldehyde or ketone to an alkyne. Palladium‐catalyzed cross‐coupling reactions of alternative metal acetylides and masked alkynes are also discussed in this section. The Tabular Survey is primarily organized in terms of the organic electrophile and then by the nature of the alkyne coupling partner. This chapter serves as the definitive review of this powerful reaction that will prove invaluable to anyone interested in this transformation.

I would like to take this opportunity to acknowledge Prof. P. Andrew Evans, who has served as the Editor‐in‐Chief and President of Organic Reactions for the past six years. During his tenure, he oversaw 15 volumes containing 32 chapters encompassing a diverse array of important organic reactions. Organic Reactions implemented several important changes to evolve with the ever‐changing landscape of modern organic chemistry under his leadership. Most significantly, chapters no longer provide comprehensive tables and references for the title reaction, rather they focus on highlighting the most relevant examples to assist the reader in selecting optimal conditions. Organic Reactions chapters will continue to provide authoritative and critical reviews of specific reactions in this new format. This new format with shorter chapters will allow volumes to appear on a more regular basis and to contain more chapters in each volume. Another key change to occur under his leadership is a modernization of the operations of Organic Reactions to maintain the high quality of chapters, while keeping the workload manageable for the editorial team. As part of this reorganization, the positions of Editor‐in‐Chief and President have been split. I am pleased to say that Evans will remain in the role of President as I take over the responsibility of Editor‐in‐Chief.

Finally, I would like to take this opportunity to acknowledge the entire Organic Reactions Editorial Board for their collective efforts in steering this chapter through the various stages of the editorial process. I would particularly like to thank Prof. Dennis Hall and Prof. André Charette who served as Responsible Editors and worked tirelessly with the authors to see the completion of this chapter. I am also deeply indebted to Dr. Danielle Soenen for her continuous efforts as the Editorial Coordinator. Her knowledge of Organic Reactions is critical to maintaining the quality and consistency of the series. Dr. Dena Lindsay (Secretary to the Editorial Board) is thanked for coordinating the contributions of the authors, editors, and publisher. In addition, the Organic Reactions enterprise could not maintain the quality of production without the meticulous efforts of Prof. Steven Weinreb (Executive Editor), Dr. Engelbert Ciganek (Editorial Advisor), Dr. Landy Blasdel (Processing Editor), and Dr. Tina Grant (Processing Editor). I would also like to thank Dr. Michael Evans and Dr. Joseph Ward for maintaining our web presence (organicreactions.org). Finally, thank you to Prof. Barry Snider (Secretary) for keeping everyone on task and Dr. Jeffery Press (Treasurer) and Prof. Robert Maleczka (Treasurer‐Elect) for ensuring Organic Reactions continues to remain fiscally viable.

In taking on the role of Editor‐in‐Chief, I am honored and humbled to follow in the footsteps of Roger Adams, Arthur Cope, William Dauben, Andrew Kende, Leo Paquette, Larry Overman, Scott Denmark, and P. Andrew Evans. Their efforts along with all past and present members of the Board of Editors and Board of Directors have ensured the enduring quality of Organic Reactions. The distinctive format of the chapters, along with the curated tables of examples, makes this series of reviews a unique and exceptionally valuable resource to the practicing synthetic organic chemist.

Kevin H. Shaughnessy

Tuscaloosa, Alabama

USA

1A HALF CENTURY OF THE SONOGASHIRA REACTION

STEPHANIE FRANKENBERGER, DOMINIK WENDINGER, AND ALEXANDER SCHERER

Department of Chemistry and Pharmacy, Friedrich‐Alexander‐University Erlangen‐Nuremberg (FAU), Nikolaus‐Fiebiger‐Strasse 10, 91058, Erlangen, Germany

KENKICHI SONOGASHIRA

Osaka City University, 3‐3‐138, Sugimoto

Sumiyoshi‐ku, Osaka 558‐8585, Japan

RIK R. TYKWINSKI

Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G 2G2, Canada

Edited by DENNIS G. HALL AND ANDRÉ CHARETTE

CONTENTS

ACKNOWLEDGMENTS

INTRODUCTION

MECHANISM AND STEREOCHEMISTRY

General Catalytic Cycle for Pd/Cu‐Catalyzed Sonogashira Reactions

General Catalytic Cycle for Cu‐Free, Pd‐Catalyzed Sonogashira Reactions

Other Mechanistic Considerations

Nature of the Electrophile

Nature of the Catalyst

Role of the Base

Stereochemistry

SCOPE AND LIMITATIONS

The Electrophile

Aryl Halides and Triflates

Heteroaryl Halides and Triflates

Alkenyl Halides and Triflates

Miscellaneous/Alternative Electrophiles

Organometallic Compounds

Inorganic Compounds

Leaving Groups Beyond Halides and Triflates

The Alkyne

Acetylene

Protected Acetylene

Functionalized Alkynes

Polyynes

APPLICATIONS TO SYNTHESIS

Synthesis of Derivatives of Phthalocyanines and Porphyrins

Synthesis of Conjugated Organic Compounds

Synthesis of Cyclic Compounds

Synthesis of Natural Products/Bioactive Compounds

Application to a Kilo‐Scale Synthesis of a Drug Intermediate

COMPARISON WITH OTHER METHODS

Alternative Methods for Constructing an Alkyne Linked to an Aryl or Alkenyl Group

Conversion of a Carbonyl Compound to an Alkyne

Fritsch–Buttenberg–Wiechell Rearrangement

Corey–Fuchs Reaction

Colvin Rearrangement

Seyferth–Gilbert Homologation

Bestmann–Ohira Reaction

Pd‐Catalyzed Cross‐Coupling Reactions of Alternative Metal Acetylides and Masked Alkynes to Aryl or Alkenyl Electrophiles

Pd‐Catalyzed Cross‐Coupling Reactions of Other Metal Acetylides

Boron Reagents

Magnesium Reagents

Tin Reagents

Zinc Reagents

Other Metal Reagents

Masked/Protected Alkynes

Acetone as a Masking Group

Calcium Carbide

Carboxylic Acid Groups

Trialkylsilyl Groups

Alkyne Metathesis

EXPERIMENTAL CONDITIONS

Solvents and Bases

Catalyst Systems and Ligands

EXPERIMENTAL PROCEDURES

2‐(Trimethylsilylethynyl)aniline [Cross Coupling of Trimethylsilylacetylene with an Aryl Iodide Using Pd(II) and Cu(I)]

4‐(4‐Bromophenyl)‐2‐methyl‐3‐butyn‐2‐ol [Cross Coupling of 2‐Methyl‐3‐butyn‐2‐ol with an Aryl Bromide Using Pd(II) and Cu(I)]

1‐{4[(4‐Cyanophenyl)ethynyl]phenyl}ethanone [Sequential, One‐Pot Double Arylation of Trimethylsilylacetylene]

3,6‐Bis(benzoylbiphenyl)ethynyl‐9‐tetradecylcarbazole [Cross Coupling of a Diethynylcarbazole with a Bromobiphenyl Using Pd

2

(dba)

3

, PPh

3

, and CuI]

3,6‐Diethynyl‐9‐tetradecylcarbazole [Diethynylation of a Diiodocarbazole by Cross Coupling with Trimethylsilylacetylene Followed by Desilylation]

[(3

Z

)‐4,5,5,5‐Tetrafluoro‐3‐penten‐1‐yn‐1‐yl]benzene [Cross Coupling of a 1‐Alkyne with an Alkenyl Iodide Using Pd(OAc)

2

, PPh

3

, and CuI]

2‐Chloro‐1‐decen‐3‐yne [Cross Coupling of 1‐Octyne with an Alkenyl Chloride Using Pd(II) and Cu(I)]

7‐Methylene‐8‐hexadecyn‐6‐ol [Cross Coupling of 1‐Nonyne with an Alkenyl Bromide Using Pd(II) and Cu(I)]

(

SP

‐4‐1)‐{[Diethyl 4,4′‐{[10,20‐bis{[(

E

)‐3,4‐bis{[(

tert

‐butyl)dimethylsilyloxy]methyl}‐6‐(trimethylsilyl)hex‐3‐ene‐1,5‐diynyl}(porphine‐5,15‐diyl)bis[benzene‐1,4‐diyl(oxy)]}bis(butanoato)](2‐)‐

N

21,

N

22,

N

23,

N

24}zinc [Cross Coupling of a 1‐Alkyne with a Diiodoporphyrin Using Pd(II), AsPh

3

, and Cu(I)]

Poly(aryleneethynylene) [Polymer Synthesis by Cross Coupling of a 1,4‐Diethynylarene and a 1,4‐Diiodoarene]

9‐[4,7‐Bis(diphenylmethylene)‐2,5,8‐cyclononatriyn‐1‐ylidene]‐9

H

‐fluorene [Intramolecular Cross Coupling of a 1‐Alkyne and an Alkenyl Bromide]

Tripeptide 97 [Intramolecular Cross Coupling of a 1‐Alkyne and an Aryl iodide]

LIST OF ABBREVIATIONS

TABULAR SURVEY

Chart 1. Catalysts Used in the Tables

Chart 2. Ligands Used in the Tables

Chart 3. Functional Group Acronyms Used in the Tables

Table 1. Cross Coupling of Aryl Electrophiles

A. With Representative Terminal Aryl Alkynes

B. With Representative Terminal Heteroaryl Alkynes

C. With Representative Terminal Enynes

D. With Representative Terminal Aliphatic Alkynes

E. With Representative Terminal Trialkylsilyl Alkynes

F. With Representative Miscellaneous Terminal Alkynes

Table 2. Cross Coupling of Multifunctional Aryl Electrophiles

A. With Representative Terminal Aryl Alkynes

B. With Representative Terminal Heteroaryl Alkynes

C. With Representative Terminal Enynes

D. With Representative Terminal Aliphatic Alkynes

E. With Representative Terminal Trialkylsilyl Alkynes

F. With Representative Miscellaneous Terminal Alkynes

Table 3. Cross Coupling of Heteroaryl Electrophiles

A. With Representative Terminal Aryl Alkynes

B. With Representative Terminal Heteroaryl Alkynes

C. With Representative Terminal Enynes

D. With Representative Terminal Aliphatic Alkynes

E. With Representative Terminal Trialkylsilyl Alkynes

F. With Representative Miscellaneous Terminal Alkynes

ACKNOWLEDGMENTS

First and foremost, we acknowledge and thank the Responsible Editors, Dennis Hall and André Charette, for the patience, advice, and help completing this monumental project. This project would not have been possible without the invaluable help of Dr. Danielle Soenen. We are grateful for funding from the Natural Sciences and Engineering Research Council of Canada (NSERC) and the Deutsche Forschungsgemeinschaft (SFB 953, “Synthetic Carbon Allotropes”).

INTRODUCTION

Conjugated acetylenic compounds are valuable intermediates in the synthesis of natural products, pharmaceuticals, and organic molecular materials. These compounds are frequently prepared via one of two general classes of Pd‐catalyzed cross‐coupling reactions between sp2‐ and sp‐hybridized carbon atoms. The most common approach utilizes the cross coupling of unsaturated organic halides (or pseudo‐halides) with terminal alkynes. Alternatively, processes that use preformed alkynylmetal reagents can also be employed (Scheme 1).

Scheme 1

Seminal reports of Pd‐catalyzed coupling reactions between sp2‐hybridized carbon halides and terminal alkynes were independently reported by three laboratories (Scheme 2).1–3 Two of these methods use a palladium catalyst1,2 and have been developed as extensions of the Heck reaction. The third method is the Sonogashira reaction,3 which utilizes a combination of palladium(0) and copper(I) catalysts for alkynylations4 of aryl and alkenyl electrophiles. Although this process is analogous to the copper‐catalyzed Stephens–Castro reaction,5 the use of milder reaction conditions, combined with extensive catalyst development, has expanded the scope of the Sonogashira reaction far beyond that achievable with alkynylations based solely on copper catalysis.

Scheme 2

The Sonogashira reaction is broadly used