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- Herausgeber: Wiley-VCH Verlag GmbH & Co. KGaA
- Kategorie: Wissenschaft und neue Technologien
- Sprache: Englisch
The first handbook on this emerging field provides a comprehensive overview of transition metal-catalyzed coupling reactions in the presence of an oxidant. Following an introduction to the general concept and mechanism of this reaction class, the team of authors presents chapters on C-C cross-coupling reactions using organometallic partners, C-Heteroatom bond forming reactions via oxidative couplings, and C-H couplings via C-H activation. The text also covers such groundbreaking topics as recent achievements in the fields of C-C and C-X bond formation reactions as well as C-H activation involving oxidative couplings.
With its novel and concise approach towards important building blocks in organic chemistry and its focus on synthetic applications, this handbook is of great interest to all synthetic chemists in academia and industry alike.
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Seitenzahl: 260
Veröffentlichungsjahr: 2016
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Table of Contents
Cover
Title Page
Copyright
Chapter 1: Oxidative Coupling – Bonding between Two Nucleophiles
1.1 Introduction/General
References
Chapter 2: Organometals as Nucleophiles
2.1 Classification and Applications of Organometallic Reagents
2.2 Csp–M and Csp–M as Nucleophiles
2.3 Csp–M and Csp
2
–M as Nucleophiles
2.4 Csp–M and Csp
3
–M as Nucleophiles
2.5 Csp
2
–M and Csp
2
–M as Nucleophiles
2.6 Csp
2
–M and Csp
3
–M as Nucleophiles
2.7 Csp
3
–M and Csp
3
–M as Nucleophiles
2.8 Conclusions
Acknowledgments
References
Chapter 3: Oxidative Couplings Involving the Cleavage of C–H Bonds
3.1 Theoretical Understandings and Methods in C–H Bond Functionalization
3.2 Oxidative Couplings between Organometals and Hydrocarbons
3.3 Oxidative Couplings between Two Hydrocarbons
3.4 Conclusions
References
Chapter 4: Bonding Including Heteroatoms via Oxidative Coupling
4.1 Introduction
4.2 Oxidative C–O Bond Formation
4.3 Oxidative C–N Bond Formation
4.4 Oxidative C–Halo Bond Formation
4.5 Oxidative C–S Bond Formation
4.6 Oxidative C–P Bond Formation
4.7 Oxidative C–B Bond Formation
References
Chapter 5: Oxidative Radical Couplings
5.1 Introduction
5.2 Oxidative Radical C–C Couplings
5.3 Oxidative Radical C–C Couplings through Cascade Process
5.4 Oxidative Radical C–C Couplings via C–C(N) Bond Cleavage
References
Index
End User License Agreement
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Guide
Cover
Table of Contents
Begin Reading
List of Illustrations
Chapter 1: Oxidative Coupling – Bonding between Two Nucleophiles
Scheme 1.1 Bond formation modes of classic cross-coupling and oxidative cross-coupling.
Scheme 1.2 Comparison between classic synthetic route and oxidative cross-coupling.
Scheme 1.3 General catalytic cycle of palladium-catalyzed oxidative cross-coupling reactions.
Chapter 2: Organometals as Nucleophiles
Scheme 2.1 Typical elements in organometallic reagents.
Scheme 2.2 Different oxidative cross-coupling reactions.
Scheme 2.3
Scheme 2.4
Scheme 2.5
Scheme 2.6
Scheme 2.7 Triynes from TBS protected diynes.
Scheme 2.8 Oxidative homocoupling of alkynylsilanes to form diynes.
Scheme 2.9 Pd catalyzed homocoupling of alkylylsilanes without activator.
Scheme 2.10 Homocoupling of alkynyltrimethyltin reagent to form polymers.
Scheme 2.11 Mechanism of oxidative homocoupling of alkynyltin reagents.
Scheme 2.12 Palladium-catalyzed homocoupling of alkynylborates.
Scheme 2.13 Oxidative homocoupling of alkynyltrifluoroborates.
Scheme 2.14 Proposed mechanism of the oxidative homocoupling of alkynyltrifluoroborates.
Scheme 2.15 Manganese-catalyzed homocoupling of alkynyl Grignard reagents.
Scheme 2.16 Proposed mechanism of the Mn-catalyzed reaction.
Scheme 2.17 Oxidative cross-coupling of alkynyl magnesium reagents.
Scheme 2.18 Iron catalyzed homocoupling of alkynyl Grignard reagents.
Scheme 2.19 Knochel's protocol to form diynes.
Scheme 2.20 Homocoupling of alkynyl Grignard reagents without transition metals.
Scheme 2.21 Homocoupling reaction of functionalized
n
-butyl alkynyltellurides.
Scheme 2.22 Proposed mechanism for the homocoupling of functionalized
n
-butyl alkynyltellurides.
Scheme 2.23 General mechanism of Sonogashira coupling reaction.
Scheme 2.24 Oxidative coupling between aryl magnesium reagents and alkynyl lithium.
Scheme 2.25 Examples of substrate scope.
Scheme 2.26 Mechanism of the Mn-catalyzed oxidative cross-coupling.
Scheme 2.27 Manganese-catalyzed oxidative cross-coupling between aryl and alkynyl Grignard reagents.
Scheme 2.28 Differences of reaction rate for aryl and alkynyl Grignard reagents.
Scheme 2.29 Substrate scope.
Scheme 2.30 Oxidative cross-coupling between alkyl zinc and alkynyl tin.
Scheme 2.31 Mechanism.
Scheme 2.32 CO accelerated oxidative cross-coupling of alkyl zinc reagents and terminal alkynes.
Scheme 2.33
Scheme 2.34 Vanadium catalyzed synthesis of unsymmetrical biaryls.
Scheme 2.35 Iron-catalyzed oxidative cross-coupling to form biaryls.
Scheme 2.36 Ligand effect in Pd catalyzed oxidative cross-coupling.
Scheme 2.37 Substrate scope of the oxidative cross-coupling.
Scheme 2.38 Csp
2
–Zn cross-coupled with Csp
3
–In.
Scheme 2.39 Mechanism for the coupling of Csp
2
–Zn and Csp
3
–In.
Scheme 2.40
Scheme 2.41
Scheme 2.42
Scheme 2.43 Homocoupling of alkyl zinc reagents.
Scheme 2.44 β-H elimination effect.
Scheme 2.45 Mechanism of the homocoupling.
Scheme 2.46
Chapter 3: Oxidative Couplings Involving the Cleavage of C–H Bonds
Scheme 3.1 Five typical mechanisms for inner-sphere transition metal-mediated C–H bond cleavage.
Scheme 3.2 Two typical mechanisms for outer-sphere transition metal-mediated C–H bond cleavage.
Scheme 3.3 Oxidative addition between iridium and C–H bond in simple alkanes.
Scheme 3.4 Mechanism for the aromatic borylation catalyzed by iridium species.
Scheme 3.5 Ru(0)-catalyzed
ortho
-C–H functionalization via oxidative addition.
Scheme 3.6 Electrophilic aromatic mercuration.
Scheme 3.7 The Fujiwara–Moritani reaction.
Scheme 3.8 Direct C-2 arylation of indoles with aryl iodides at room temperature.
Scheme 3.9 σ-Bond metathesis pathway.
Scheme 3.10 Representative mechanism for the acetolysis of diphenylmercury(II).
Scheme 3.11 Mechanism for the cyclometalation of DMBA-H with palladium.
Scheme 3.12 Proposed catalytic cycle for direct arylation via CMD mechanism.
Scheme 3.13 Addition of methane to [ZrN] double bond.
Scheme 3.14 Biomimetic C–H oxidation of cyclohexane using nonheme Fe(II) complex.
Scheme 3.15 Catalytic cycle for metal-catalyzed carbenoid insertion into a C–H bond.
Scheme 3.16 Rh
2
(4
S
-MEOX)
4
-catalyzed stereoselective carbenoid insertion into a C–H bond.
Scheme 3.17 Rh
2
(
S
-NTTL)
4
-catalyzed stereoselective nitrenoid insertion into a C–H bond.
Scheme 3.18 Total synthesis of (−)-tetrodotoxin via both carbenoid and nitrenoid insertion reactions.
Scheme 3.19 Directed C–H bond functionalization.
Scheme 3.20 Preparation of celecoxib analogs via divergent C–H functionalization.
Scheme 3.21
meta
-Selective C–H functionalization approaches.
Scheme 3.22 Directing groups for the Pd-catalyzed C(sp
3
)–H functionalization.
Scheme 3.23 Pd-catalyzed enantioselective C–H functionalization.
Scheme 3.24 C–H borylation of disubstituted arenes.
Scheme 3.25 Overview of the C–H functionalization via ionic intermediates.
Scheme 3.26 α-Cyanation of amines via iminium cation.
Scheme 3.27 Copper-catalyzed CDC α-alkynylation of amine.
Scheme 3.28 General mechanism of copper-catalyzed CDC α-alkynylation of amine.
Scheme 3.29 Intramolecular radical reactions.
Scheme 3.30 C–H functionalization via radical intermediates.
Scheme 3.31 Transition metal-catalyzed radical oxidative cross-coupling reactions.
Scheme 3.32 Amine-catalyzed enantioselective α-arylation of aldehydes.
Scheme 3.33 Proposed mechanism for amine-catalyzed enantioselective α-arylation.
Scheme 3.34 Photoredox-catalyzed C–H arylation reaction.
Scheme 3.35 C(sp)–C(sp
3
) oxidative coupling between terminal alkynes and alkylzinc reagents.
Scheme 3.36 Oxidative coupling between terminal alkynes and cuprous cyanide.
Scheme 3.37 Copper-mediated aerobic trifluoromethylation of terminal alkynes.
Scheme 3.38 Oxidative cross-coupling between Csp
2
–H and organometals.
Scheme 3.39 Rh-catalyzed oxidative coupling between 2-phenylpridine and aryl stannanes.
Scheme 3.40 Stoichiometric experiments.
Scheme 3.41 Oxidative cross-coupling between directing-group-containing arenes and alkylstannane reagents.
Scheme 3.42 Pd-catalyzed oxidative coupling between simple arenes and arylstannanes.
Scheme 3.43 Pd-catalyzed oxidative cross-coupling of pyridine-directed arenes with both methylboroxine and alkylboronic acids.
Scheme 3.44 Pd-catalyzed oxidative coupling of benzoic acids/aryl acetic acids with aryltrifluoroborates.
Scheme 3.45 Pd-catalyzed oxidative cross-coupling between arylboronic acids and acetamido-containing arenes.
Scheme 3.46 Pd-catalyzed oxidative coupling of electron-rich arenes with arylboronic acid.
Scheme 3.47 Mn-mediated oxidative coupling of simple arenes with arylboronic acid.
Scheme 3.48 Cu-promoted oxidative cross-coupling of electron-rich arenes and arylboronic acids.
Scheme 3.49 Fe-mediated oxidative coupling of unactivated arenes with arylboronic acid.
Scheme 3.50 Fe-mediated oxidative coupling of
N
-heterocyclics with arylboronic acid.
Scheme 3.51 Fe-catalyzed oxidative coupling of arylboronic acids with benzene derivatives.
Scheme 3.52 Pd-catalyzed oxidative arylation of electron-deficient arenes with arylboronic acids.
Scheme 3.53 Ni-catalyzed oxidative cross-coupling between heteroarenes and arylboronic acids.
Scheme 3.54 Pd-catalyzed oxidative cross-coupling between polycyclic aromatic hydrocarbons and arylboroxins.
Scheme 3.55 Synthesis of extended PAHs.
Scheme 3.56 Pd-catalyzed oxidative C4-arylation of thiophenes with arylboronic acids.
Scheme 3.57 Pd-catalyzed oxidative coupling between acetamido-group-directing
ortho
-C–H bond and trialkoxyarylsilanes.
Scheme 3.58 Ni-catalyzed oxidative coupling between heteroarenes and arylsilanes/alkenylsilane.
Scheme 3.59 Pd-catalyzed oxidative coupling between thiophenes and benzothiophenes and aryltrimethylsilanes.
Scheme 3.60 Fe-catalyzed oxidative cross-couplings between Csp
2
–H and organozinc reagents.
Scheme 3.61 Fe-catalyzed oxidative cross-couplings between aryl imines and organozinc reagents.
Scheme 3.62 Fe-catalyzed oxidative couplings between alkenes and organozinc reagents.
Scheme 3.63 Fe-catalyzed oxidative couplings between alkenes and Grignard reagents.
Scheme 3.64 Co-catalyzed oxidative cross-couplings between benzo[
h
]quinoline and Grignard reagents.
Scheme 3.65 Co-catalyzed oxidative couplings between arylpyridines and Grignard reagents.
Scheme 3.66 Ni-catalyzed alkenylation of arylboronic acids with olefins.
Scheme 3.67 Cyanation of Csp
3
–H bonds besides N atoms.
Scheme 3.68 Arylation of Csp
3
–H bonds.
Scheme 3.69 Arylation of unactivated Csp
3
–H bonds.
Scheme 3.70 Glaser coupling and Glaser–Hay coupling.
Scheme 3.71 Dimeric copper acetylide mechanism.
Scheme 3.72 Cu(II)–Cu(I) synergistic cooperation to lead the cleavage of acetylene C–H bond and oxidative homocoupling.
Scheme 3.73 Ni- and Cu-catalyzed oxidative cross-coupling of different terminal alkynes.
Scheme 3.74 Gold-catalyzed oxidative cross-coupling of different terminal alkynes.
Scheme 3.75 Gold-mediated coupling between arenes and terminal alkynes.
Scheme 3.76 Gold-catalyzed alkynylation of electron-rich arenes and alkenes.
Scheme 3.77 Proposed mechanism for the Au-catalyzed alkynylation of electron-rich arenes.
Scheme 3.78 Pd-catalyzed C2-alkynylation of N-protected indoles with terminal alkynes.
Scheme 3.79 Direct alkynylation of thiophenes and other aromatic heterocycles.
Scheme 3.80 Direct oxidative C–H alkynylation of electron-poor (hetero)arenes.
Scheme 3.81 Directed C–H alkynylation of unactivated (hetero)arenes.
Scheme 3.82 Oxidative coupling between acetylene C–H bonds and C(sp
3
)–H bonds adjacent to heteroatoms.
Scheme 3.83 Tandem oxidative C(sp
3
)–H/C(sp)–H alkynylation and cyclization.
Scheme 3.84 Oxidative cross-coupling using Csp
2
–H and Csp
2
–H as nucleophiles.
Scheme 3.85 Oxidative cross-coupling between benzoquinoline (Bzq) and benzene.
Scheme 3.86 Oxidative coupling of unactivated arenes with arenes containing an acetamino group.
Scheme 3.87 Oxidative coupling of unactivated arenes with pyridine
N
-oxides.
Scheme 3.88 Oxidative cross-coupling of different unactivated arenes.
Scheme 3.89 Pd-catalyzed oxidative C-3 arylation of indoles.
Scheme 3.90 Pd-catalyzed oxidative C-2 arylation of indoles.
Scheme 3.91 Pd-catalyzed oxidative C-2 arylation of benzofuran.
Scheme 3.92
Scheme 3.93
Scheme 3.94 Pd-catalyzed intramolecular oxidative cyclization of
N
-benzoylindoles.
Scheme 3.95 Pd-catalyzed intramolecular oxidative cyclization of diarylethers and diarylanilines.
Scheme 3.96 Pd-catalyzed one-pot synthesis of carbazoles from aryl triflates and anilines.
Scheme 3.97 Pd-catalyzed oxidative cyclization of anilides.
Scheme 3.98 Pd-catalyzed intramolecular oxidative cyclization.
Scheme 3.99 Oxidative coupling to form annulated seven-membered rings.
Scheme 3.100 Oxidative coupling to form annulated eight-membered rings.
Scheme 3.101 Represented substrates in oxidative Heck-type couplings.
Schemes 3.102 General mechanisms for Pd-catalyzed oxidative Heck-type alkenylation by intermolecular carbopalladation.
Scheme 3.103 General mechanisms for Pd-catalyzed oxidative Heck-type alkenylation by aromatic C–H palladation.
Scheme 3.104 Pd-catalyzed oxidative
ortho
-alkenylation of anilides at room temperature.
Scheme 3.105
Scheme 3.106
Scheme 3.107
Scheme 3.108
Scheme 3.109
Scheme 3.110
Scheme 3.111
Scheme 3.112
Scheme 3.113
Scheme 3.114
Scheme 3.115
Scheme 3.116
Scheme 3.117
Scheme 3.118
Scheme 3.119
Scheme 3.120
Scheme 3.121
Scheme 3.122
Scheme 3.123
Scheme 3.124
Scheme 3.125
Scheme 3.126
Scheme 3.127
Scheme 3.128
Scheme 3.129
Chapter 4: Bonding Including Heteroatoms via Oxidative Coupling
Scheme 4.1
Scheme 4.2
Scheme 4.3
Scheme 4.4
Scheme 4.5
Scheme 4.6
Scheme 4.7
Scheme 4.8
Scheme 4.9
Scheme 4.10
Scheme 4.11
Scheme 4.12
Scheme 4.13
Scheme 4.14
Scheme 4.15
Scheme 4.16
Scheme 4.17
Scheme 4.18
Scheme 4.19
Scheme 4.20
Scheme 4.21
Scheme 4.22
Scheme 4.23
Scheme 4.24
Scheme 4.25
Scheme 4.26
Scheme 4.27
Scheme 4.28
Scheme 4.29
Scheme 4.30
Scheme 4.31
Scheme 4.32
Scheme 4.33
Scheme 4.34
Scheme 4.35
Scheme 4.36
Scheme 4.37
Scheme 4.38
Scheme 4.39
Scheme 4.40
Scheme 4.41
Scheme 4.42
Scheme 4.43
Scheme 4.44
Scheme 4.45
Scheme 4.46
Scheme 4.47
Scheme 4.48
Scheme 4.49
Scheme 4.50
Scheme 4.51
Scheme 4.52
Scheme 4.53
Scheme 4.54
Scheme 4.55
Scheme 4.56
Scheme 4.57
Scheme 4.58
Scheme 4.59
Scheme 4.60
Scheme 4.61
Scheme 4.62
Scheme 4.63
Scheme 4.64
Scheme 4.65
Scheme 4.66
Scheme 4.67
Scheme 4.68
Scheme 4.69
Scheme 4.70
Scheme 4.71
Scheme 4.72
Scheme 4.73
Scheme 4.74
Scheme 4.75
Scheme 4.76
Scheme 4.77
Scheme 4.78
Scheme 4.79
Scheme 4.80
Scheme 4.81
Scheme 4.82
Scheme 4.83
Scheme 4.84
Scheme 4.85
Scheme 4.86
Chapter 5: Oxidative Radical Couplings
Scheme 5.1 Oxidative C–C couplings.
Scheme 5.2
Scheme 5.3 Alkynylation of tertiary amines.
Scheme 5.4 Alkynylation of diphenylmethane derivatives.
Scheme 5.5 Methylation of 2-phenylpyridines.
Scheme 5.6 Oxidative coupling of arenes with simple nonactivated alkanes.
Scheme 5.7 Oxidative Pd-catalyzed ortho-aroylation.
Scheme 5.8 Oxidative cross-coupling of acetanilide and toluene.
Scheme 5.9 Proposed generation of acyl radicals.
Scheme 5.10 Oxidative cross-coupling of acetanilide and toluene.
Scheme 5.11 Para-selective oxidative cross-coupling of substituted benzene with cycloalkanes.
Scheme 5.12 Oxidative cross-coupling of pyridine
N
-oxide derivatives with simple alkanes.
Scheme 5.13 Oxidative C-2 alkylation of quinoline
N
-oxides with ethers.
Scheme 5.14 Oxidative coupling of α-position sp
3
C–H in alcohols and ethers.
Scheme 5.15 Oxidative radical coupling between simple ethers and α,α-diaryl allylic alcohols.
Scheme 5.16 Proposed mechanism for oxidative radical coupling.
Scheme 5.17 Oxidative radical coupling between amides/ethers and benzene derivatives.
Scheme 5.18 Proposed mechanism for oxidative radical coupling.
Scheme 5.19 Nickel-catalyzed regioselective coupling of dioxane with indoles.
Scheme 5.20 Oxindole synthesis through Pd-catalysis or oxidative coupling.
Scheme 5.21 Cu-mediated intramolecular oxidative C–C bond formation.
Scheme 5.22 Cu-mediated oxindole synthesis.
Scheme 5.23 Proposed mechanism for oxidative radical coupling for oxindole synthesis.
Scheme 5.24 Oxidative coupling/cyclization of alkenes and 2-(pyridin-2-yl) acetate derivatives.
Scheme 5.25 Proposed mechanism for oxidative radical coupling for indolizine synthesis.
Scheme 5.26 Oxidative coupling/annulation of β-keto esters with alkenes.
Scheme 5.27 A radical addition/cyclization mechanism.
Scheme 5.28 Copper-catalyzed oxidative coupling of enones and toluenes.
Scheme 5.29 A proposed reaction pathway for the oxidative coupling.
Scheme 5.30 Oxidative coupling of benzylic C–H bonds with 1,3-dicarbonyl compounds.
Scheme 5.31 Intramolecular kinetic isotope effect.
Scheme 5.32 Fe-catalyzed alkylation of activated methylenes.
Scheme 5.33 Proposed mechanism for alkylation of activated methylenes.
Scheme 5.34 Oxidative coupling of vinylarenes with cyclic ethers.
Scheme 5.35 Oxidative cross-coupling between benzylic C–H and 1-aryl vinyl acetate.
Scheme 5.36 Oxidative radical coupling of substituted olefins and simple ethers.
Scheme 5.37 Oxidative cross-coupling of different phenols.
Scheme 5.38
Ortho
-C–H acylation of 2-arylpyridines with arylmethyl amines.
Scheme 5.39 Proposed process for generation of radical intermediates.
Scheme 5.40 Oxidative coupling of alkenes with aldehydes.
Scheme 5.41 Oxidative coupling of arenes and alkenes.
Scheme 5.42 Proposed mechanism for the oxidative cross-coupling between 1,3,5-trimethoxybenzene and diarylethylenes.
Scheme 5.43 Oxidative coupling of isonitrile with simple alkanes.
Scheme 5.44 Proposed mechanism for the free-radical addition/cyclization cascade reaction.
Scheme 5.45 Oxidative radical C–C coupling can proceed between 2-aryl phenyl isonitrile and simple alcohols.
Scheme 5.46 Coupling between 2-aryl phenyl isonitrile and dioxane.
Scheme 5.47 Functionalized oxindole synthesis via oxidative radical coupling.
Scheme 5.48 Oxidative tandem coupling of activated alkenes with carbonyl C(sp
2
)–H bonds.
Scheme 5.49 Tandem radical addition/cyclization of acrylamides and benzyl hydrocarbons.
Scheme 5.50 Proposed mechanism for the tandem radical addition/cyclization of acrylamides and benzyl hydrocarbons.
Scheme 5.51 Reaction of activated alkenes and alcohols.
Scheme 5.52 Proposed mechanism for the metal-free tandem radical addition/cyclization reaction of activated alkenes and alcohols.
Scheme 5.53 Oxidative cyclization of acrylamides with 1,3-dicarbonyls.
Scheme 5.54 Oxidative coupling of hydroxymethylacrylamide with 1,3-dicarbonyl compounds.
Scheme 5.55 Oxidative alkylarylation of acrylamides with simple alkanes.
Scheme 5.56 Reaction mechanism for free radical cascade process.
Scheme 5.57 Diacylation of coumarins.
Scheme 5.58 Decarboxylative acylation of acrylamides.
Scheme 5.59 Decarboxylative acylation of acrylamides to yield six-membered rings.
Scheme 5.60 Decarbonylative coupling of aromatic aldehydes with arenes.
Scheme 5.61 Oxidative coupling of styrenes and benzyl alcohols with arenes.
Scheme 5.62 Arylalkoxycarbonylation of
N
-aryl acrylamides.
Scheme 5.63 Radical arylalkoxycarbonylation of 2-isocyanobiphenyl.
Scheme 5.64 Arylalkoxycarbonylation of imidazoheterocycles.
List of Tables
Chapter 2: Organometals as Nucleophiles
Table 2.1 Common named organometallic reagents
Table 2.2 Selected homocoupling of tributyl(phenylacetylenyl)tin
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Aiwen Lei,Wei Shi, Chao Liu,Wei Liu, Hua Zhang, and Chuan He
Oxidative Cross-Coupling Reactions
Authors
Prof. Aiwen Lei
Wuhan University
College of Chemistry & Molecular Science
Luo-jia-shan, Wuchang
Wuhan 430072
Hubei
China
Dr. Wei Shi
Huazhong Agricultural University
Department of Chemistry
Shizishan St., Hongsham, 1
Wuhan 430070
Hubei
China
Prof. Chao Liu
Chinese Academy of Sciences
Lanzhou Institute of Chemical Physics (LICP)
Suzhou Research Institute of LICP
State Key Laboratory for Oxo Synthesis and Selective Oxidation
No.18, Tianshui Middle Road
Lanzhou 730000
P.R.China
Dr. Wei Liu
Henan University of Technology
Lipid Chemistry, College of Food Science
Lianhua Street 1
Zhengzhou 450001
China
Dr. Hua Zhang
Wuhan University
College of Chemistry & Molecular Science
Luo-jia-shan, Wuchang
Wuhan 430072
Hubei
China
Dr. Chuan He
University of Cambridge
Department of Chemistry
Lensfield Road
CB2 1EW Cambridge
United Kingdom
Cover
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Chapter 1Oxidative Coupling – Bonding between Two Nucleophiles
1.1 Introduction/General
1.1.1 What is Oxidative Cross-Coupling?
Transition-metal-catalyzed cross-coupling reactions have been developed to be a powerful tool for the construction of various chemical bonds since its initial discovery in the last century [1]. Owing to their great capacity for different types of bond formation, they have been widely applied in the areas of pharmaceuticals, agriculture, food industries, materials sciences, and so on [2]. Normally, in those classical cross-coupling reactions, bond formations occur between an electrophile and a nucleophile in the presence of a transition metal catalyst (Scheme 1.1, Eq. (1.1)) [3], in which no extra redox reagents are required for achieving the bond formation [4]. Both the electrophiles and the organometallic nucleophiles are usually obtained from pre-functionalization of their corresponding R–Hs (R equals C, N, O, S, etc.). However, with the development of modern synthetic methodology and the urgent demand for green and economical synthesis, traditional cross-couplings face great challenges on account of their inevitable drawbacks such as low atom economy and considerable generation of useless by-products [1, 5, 6]. At this point, direct bond formation between two nucleophiles, especially two hydrocarbons, would be an ideal alternative. As the coupling between two nucleophiles has to use an extra oxidant to promote bond formation, this type of couplings are named as oxidative cross-coupling (Scheme 1.1, Eq. (1.2)) [4, 7].
Scheme 1.1 Bond formation modes of classic cross-coupling and oxidative cross-coupling.
1.1.2 Why Oxidative Cross-Coupling?
Oxidative cross-couplings have gone through an extremely rapid development over the past decades, owing to their great potential for green and economic synthesis as well as considerable advantages over traditional cross-couplings, especially those couplings between two CH nucleophiles [8, 9]. Normally, nucleophiles can be divided into several classes: MX, CM, CH, or XH (X = N, O, S, etc.). In the MX group, salts such as metal halides are employed as reactants to form carbon–halogen bonds. In the C–M group, organometallic reagents serve as efficient carbon nucleophiles, which have been widely applied in transition-metal-catalyzed coupling reactions. Notably, CH or XH (X = N, O, S, etc.) nucleophiles exist extensively in nature, and they represent the most abundant nucleophiles. In the beginning, oxidative couplings focused on bond formations between two organometallic reagents under transition metal catalysis [10]. However, this bond formation mode does not meet the requirement of modern sustainable chemistry [11], since the organometallic reagents need to be derived from the corresponding hydrocarbons. In the following several years, replacing the organometallic reagents with various C–H or X–H nucleophiles to achieve greener oxidative couplings such as R1–H/R2–M2 and R1–H/R2–H dominated the research area, in which numerous outstanding works have been reported [12–15]. Especially, transition-metal-catalyzed oxidative R1–H/R2–H coupling with air or O2 as the oxidant is no doubt an ideal approach for bond formations [16, 17].
Taking the comparison between traditional cross-couplings and oxidative R1–H/R2–H couplings into account, usually, the electrophilic organohalides and the nucleophilic organometal reagents are more or less obtained from their corresponding C–H compounds in order to make the carbon site reactive enough to achieve C–C bond formation under catalytic conditions (Scheme 1.2, General Classic Synthetic Route). In this case, more reaction steps and more waste are unavoidable. Along with the development of chemical societies and the requirement for more sustainable chemical process arises the question whether C–C bond formations can be achieved directly from the C–H substrates that do not need to be pre-functionalized. It will greatly shorten the synthetic route and reduce the generation of waste. To form C–H bonds from C–H substrates, only hydrogen has to be released. Therefore, atom economy is considerably enhanced, demonstrating great potential for pharmaceutical and industrial application. Usually, an oxidant is required to accept the hydrogen; therefore, it was named as oxidative cross-coupling. Until now, various oxidants have been developed including peroxides, copper salts, silver salts, and so on [4, 7]. Oxygen gas is perhaps the most appealing oxidant for oxidative cross-couplings, as H2O is usually the side product. Recently, cross-coupling with hydrogen revolution has been demonstrated to achieve C–C and C–heteroatom bond formations in the absence of an external oxidant [18–24]. Those developments put forward the area of oxidative cross-coupling into more practical and more environmentally benign processes.
Scheme 1.2 Comparison between classic synthetic route and oxidative cross-coupling.
1.1.3 How Does Oxidative Cross-Coupling Work?
In the initially reported oxidative cross-coupling reactions, palladium catalysis was predominantly used for a long time for achieving various bond formations between two nucleophiles. For the mechanistic aspect, the general catalytic cycle of palladium-catalyzed oxidative coupling reactions can be elucidated from Scheme 1.3 [25]. As shown in Scheme 1.3, the catalytic cycle generally starts from a high valent Pd species. Consequent transmetalation of two different nucleophiles with the Pd species affords a Nu1–Pd–Nu2 intermediate, followed by reductive elimination to afford the coupling product Nu1–Nu2 and release of a low valent palladium species [Pdn], which can be reoxidized by a proper oxidant to regenerate the [Pdn+2] species. From the catalytic cycle in Scheme 1.3, we can see that both of the nucleophiles are involved in the final product, while the oxidant only acts as the electron acceptor to reoxidize the [Pdn] species without going into the coupling product. Generally, most of the palladium-catalyzed reactions are not supposed to be radical processes. Along with the development of oxidative cross-couplings, more and more first-row transition metal catalysis has been discovered, in which single-electron transfer (SET) processes become common phenomena.
Scheme 1.3 General catalytic cycle of palladium-catalyzed oxidative cross-coupling reactions.
1.1.4 Development and Outlook
Although oxidative cross-couplings between two nucleophiles form a still “young” research field compared to traditional cross-couplings, numerous excellent works have been reported on oxidative cross-couplings between two different hydrocarbons. In addition, several comprehensive reviews have been reported to summarize the recent advances in oxidative couplings between two C–H or X–H nucleophiles. However, challenges still remain in this research area. As hydrocarbons usually have different reactive C–H bonds, achieving chemoselective and regioselective C–H functionalization is still a challenging task. Moreover, understanding of this concept is still superficial and incomplete, and the mechanistic study in this area is still in its primary stage. In addition, developing mild and efficient transition-metal-catalyzed oxidative couplings between two C–H or X–H nucleophiles with air or O2 as the terminal oxidant is still in urgent demand. Further, external-oxidant-free oxidative cross-coupling between two hydrocarbons with liberation of hydrogen gas would also be a promising direction for oxidative cross-couplings.
References
1. de Meijere, A. and Diederich, F. (2004)
Metal-Catalyzed Cross-Coupling Reactions
; 2nd, completely rev. and enl. ed.;, Wiley-VCH, Weinheim.
2. Beller, M. and Bolm, C. (2004)
Transition Metals for Organic Synthesis: Building Blocks and Fine Chemicals
; 2nd rev. and enl. ed.;, Wiley-VCH, Weinheim.
3. Hartwig, J.F. (2010)
Organotransition Metal Chemistry: From Bonding to Catalysis
, University Science Books, Sausalito, California.
4. Liu, C., Zhang, H., Shi, W., and Lei, A. (2011) Bond formations between two nucleophiles: transition metal catalyzed oxidative cross-coupling reactions.
Chem. Rev.
,
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, 1780–1824.
