Green oxidation in organic synthesis

534 Pages·2019·9.171 MB·English

by  Ning Jiao&Shannon S. Stahl

Green Oxidation in Organic Synthesis

Green Oxidation in Organic Synthesis
Edited by
Ning Jiao
Peking University
Beijing, China
Shannon S. Stahl
University of Wisconsin‐Madison
Madison, WI, USA
This edition first published 2019
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Library of Congress Cataloging‐in‐Publication Data
Names: Jiao, Ning, 1976– editor. | Stahl, Shannon S., 1970– editor.
Title: Green oxidation in organic synthesis / edited by Ning Jiao (Peking University, Beijing, China),
Shannon S. Stahl (University of Wisconsin-Madison, Madison, US).
Description: First edition. | Hoboken, NJ : Wiley, 2019. | Includes bibliographical
references and index. |
Identifiers: LCCN 2019008186 (print) | LCCN 2019015930 (ebook) |
ISBN 9781119304494 (Adobe PDF) | ISBN 9781119304043 (ePub) |
ISBN 9781119304166 (hardback)
Subjects: LCSH: Organic compounds–Synthesis. | Green chemistry. | Oxidation.
Classification: LCC QD262 (ebook) | LCC QD262 .G66485 2019 (print) | DDC 547/.2–dc23
LC record available at https://lccn.loc.gov/2019008186
Cover design: Wiley
Cover image: © Sebastian Arning/EyeEm/Getty Images
Set in 10/12pt Warnock by SPi Global, Pondicherry, India
10 9 8 7 6 5 4 3 2 1
v
Contents
Preface xiii
List of Contributors xv
1 Green Oxidative: Synthesis of Alcohols and Phenols 1
Tianlei Li, Tianlong Lan, Liguo Wang, and Yu Rao
1.1 Introduction 1
1.2 C─H Hydroxylation via Aerobic Oxidant 1
1.2.1 Synthesis of Phenols by C(sp2)‐H Hydroxylation 2
1.2.2 Synthesis of Alcohol by C(sp3)‐H Hydroxylation 6
1.2.3 Oxidative Aromatization for Synthesis of Phenols 10
1.2.4 Oxygenation of Alkenes for Synthesis of Alcohols 13
1.3 C─H Hydroxylation via Hydrogen Peroxide 19
1.3.1 Synthesis of Phenols by C(sp2)‐H Hydroxylation 19
1.3.2 Synthesis of Alcohol by C(sp3)‐H Hydroxylation 22
1.4 Photocatalytic Oxidation for Synthesis of Alcohols and Phenols 28
1.5 Enzymatic Oxidation and Electrochemical Oxidation for Synthesis
of Alcohols 31
1.6 Conclusion and Perspectives 32
References 33
2 Green Oxidative Synthesis of Aldehydes and Ketones 35
Yoshiharu Iwabuchi
2.1 Introduction 35
2.2 Overview of Oxidatively Active Species Employed for Green Synthesis
of Carbonyl Compounds 36
2.3 Perspectives on the Structures of Catalytic Aerobic Oxidation Reactions 38
2.4 Oxidation of Alkanes 39
2.4.1 Autoxidation Approach 39
2.4.1.1 Transition Metal‐Catalyzed Autoxidation 40
2.4.1.2 Organocatalytic Autoxidation Approaches 42
2.4.2 Metal Oxide‐Catalyzed Aerobic Oxidation 45
2.4.3 Bio‐Inspired Approaches Using Metal Oxide Catalysis 46
2.4.3.1 Reductive Activation of Dioxygen at Iron Center: Gif System 48
2.4.3.2 Transition Metal‐Catalyzed Aerobic Oxidation of Alkanes Using
Aldehydes as Co‐Reductants 48
vi Contents
2.4.3.3 Transition Metal-Catalyzed Activation of Hydrogen Peroxide for
Oxygen Atom Transfer 49
2.4.3.4 Non‐Porphyrinic Iron Catalysts 49
2.5 Oxidation of Alkenes 50
2.5.1 Oxygenation at the Allylic Position of Alkene 52
2.5.1.1 Type 1 Allylic Oxygenation 53
2.5.1.2 Type 2 Allylic Oxygenation Mediated by 1O (Schenck‐ene Reaction) 54
2
2.5.2 Oxygenation via Partial Cleavage of the C═C Double Bond 56
2.5.2.1 Wacker‐Type Oxidation 56
2.5.2.2 Overcoming the Oxidant Problem: Use of O as the Solo Oxidant 58
2
2.5.2.3 The Anti‐Markovnikov Wacker‐Type Oxidation 58
2.5.2.4 Wacker‐Type Oxidation 60
2.5.2.5 Heterogeneous Catalysts for Wacker Reactions 60
2.5.3 Oxygenation via Full Cleavage of the C═C Double Bond 60
2.5.3.1 Ozonolysis 60
2.5.3.2 Organocatalytic Aerobic Oxidative Cleavage of C═C Double Bond 64
2.6 Oxidation of Alcohols 65
2.6.1 Platinum‐Group‐Metal‐Catalyzed Aerobic Oxidation 66
2.6.2 Palladium(II)‐Catalyzed Aerobic Oxidation 67
2.6.3 Cu‐Catalyzed Aerobic Alcohol Oxidation 68
2.6.4 Transition Metal-Catalyzed Alcohol Oxidation with H O 71
2 2
2.6.5 Heterogeneous Catalysts for Alcohol Oxidation 73
References 73
3 Green Oxidative Synthesis of Ethers, Esters, and Organic Halides 79
Lu Ouyang, Wanqing Wu, and Huanfeng Jiang
3.1 Introduction 79
3.2 Green Oxidative Synthesis of Ethers 80
3.2.1 Intramolecular Cycloetherification 81
3.2.2 Intermolecular Etherification 82
3.2.2.1 Auxiliary‐Assisted Alkoxylation or Phenoxylation via Dehydrogenative
Cross‐Coupling 82
3.2.2.2 Decarboxylative Etherification 84
3.2.2.3 Chan–Evans–Lam‐Type Etherification 84
3.2.2.4 Nucleopalladation Triggered Etherification Reactions 86
3.2.2.5 Other Etherification Reactions 87
3.3 Green Oxidative Synthesis of Esters 89
3.3.1 Oxidation of Alcohols and Aldehydes to Esters 89
3.3.2 Oxidative Carbonylation to Esters 91
3.3.3 Acyloxylation 94
3.3.3.1 Acetoxylation 94
3.3.3.2 Acyloxylation of Benzyl 100
3.3.4 Carboesterification of Alkenes and Alkynes 101
3.3.5 Esterification via Oxidative Cleavage of C─C Bonds 103
3.3.5.1 Esterifications of Arylacetonitriles via Oxidative Cleavage
of C─CN Bonds 103
Contents vii
3.3.5.2 Esterification of Simple Ketones via Oxidative Cleavage
of C(CO)–C(Alkyl) Bonds 103
3.3.5.3 Esterification of Alkynes via Oxidative Cleavage of C─C Triple Bonds 103
3.4 Green Oxidative Synthesis of Organic Halides 104
3.4.1 Catalyzed/Noncatalyzed Oxidative Halogenation with Hydrogen
Peroxide 106
3.4.1.1 Chlorination 106
3.4.1.2 Bromination 106
3.4.1.3 Iodination 107
3.4.1.4 Fluorination 107
3.4.2 Aerobic Oxidative Halogenation 107
3.4.2.1 Oxidative Halogenation of Arenes or Alkenes 108
3.4.2.2 Oxidative Halogenation of Alkynes‐Halopalladation Reaction 110
3.5 Conclusions and Outlook 115
References 115
4 Green Oxidative Synthesis of Epoxides 123
Miquel Costas
4.1 Introduction 123
4.1.1 Scope of the Chapter 125
4.2 Metal‐Catalyzed Epoxidation with O 125
2
4.2.1 Metal‐Catalyzed Epoxidations with O 125
2
4.2.2 Epoxidations with O in the Absence of a Cosubstrate 125
2
4.2.3 Epoxidations with O in the Presence of a Cosubstrate 126
2
4.3 Metal‐Catalyzed Epoxidation with H O 130
2 2
4.3.1 Heterogeneous Systems and Polyoxometallate Catalyzed Epoxidations 131
4.3.1.1 Catalysts Based in Peroxotungstate and Peroxomolybdate Species 131
4.3.1.2 Catalysts Based in Transition Metal‐Substituted Polyoxometallates 134
4.3.2 Manganese-Catalyzed Epoxidations 135
4.3.3 Asymmetric Epoxidations with Manganese Catalysts 140
4.3.4 Iron‐Catalyzed Epoxidation 143
4.3.5 Epoxidations with Iron Catalysts Prepared In Situ 145
4.3.6 Epoxidation with Well‐Defined Iron Coordination Complexes 147
4.3.7 Asymmetric Epoxidations with Iron Catalysts 147
4.4 Future Perspectives 150
References 153
5 Green Oxidative Synthesis of Carboxylic Acids 159
Mingxin Liu and Chao‐Jun Li
5.1 Oxidation of Aldehyde 159
5.1.1 Historic Methods and Challenges for Aldehyde Oxidation 159
5.1.2 Enzymatic Oxidation of Aldehyde 162
5.1.3 New Oxidants for Catalytic Aldehyde Oxidation 163
5.1.4 Catalyzed Aerobic Oxidation of Aldehyde 166
5.2 Oxidation of C─H 172
5.3 Oxidative Cleavage of C─C or C═C 173
5.3.1 Oxidative Cleavage of C═C 173
viii Contents
5.3.2 Oxidative Cleavage of 1,2‐Diol 176
5.3.2.1 Oxygen as Oxidant 176
5.3.2.2 Peroxides as Oxidants 178
5.4 Conclusion 179
References 179
6 Green Oxidative Synthesis of Amines, Amides, and Imines 181
Hong Yi, Tianyi Liu, Zilu Tang, Atul K. Singh, and Aiwen Lei
6.1 Brief Introduction 181
6.2 Green Oxidative Synthesis of Amines 181
6.2.1 Direct Amination of C(sp2)─H Bonds 182
6.2.2 Direct Amination of C(sp3)─H Bonds 184
6.2.3 Direct Amination of C(sp)─H Bonds 185
6.3 Green Oxidative Synthesis of Amides 185
6.3.1 Oxidative Amidation of Aldehydes with Amines 186
6.3.2 Oxidative Amidation of Alcohols with Amines 187
6.3.3 Oxidative Carbonylation for Amide Synthesis 188
6.3.4 Others 179
6.4 Green Oxidative Synthesis of Imines 190
6.4.1 Oxidative Cross‐Coupling of Alcohols with Amines 191
6.4.2 Oxidative Coupling of Primary Amines to Imines 192
6.4.2.1 Copper Catalysis 192
6.4.2.2 Iron Catalysis 193
6.4.2.3 Cobalt Catalysis 193
6.4.2.4 Quinone‐Based Catalysts 193
6.4.2.5 Photocatalysis 194
6.4.2.6 AIBN as the Catalyst 194
6.4.3 Oxidative Dehydrogenation of Secondary Amines 194
6.5 Conclusions 195
References 195
7 Green Oxidative Synthesis of Nitriles 199
Laura M. Dornan, Qun Cao, and Mark J. Muldoon
7.1 Introduction 199
7.2 Nitriles from Alcohols and Aldehydes 200
7.2.1 Ammonia as the Nitrogen Source 200
7.2.1.1 Heterogeneous Catalysis 200
7.2.1.2 Homogeneous Catalysis 202
7.2.2 Oxidative Reactions of Aromatic Alcohols or Aldehydes
with Acetonitrile 205
7.3 Nitriles from Amines 207
7.4 Nitriles via C─H and C─C Bond Cleavage Reactions 209
7.4.1 Nitriles from Alkynes 210
7.4.2 Nitriles from Alkenes 210
7.4.3 Cleavage of C─C Bonds in Oxygenated Substrates 212
7.4.4 Cyanation of Arenes Using Acetonitrile or N,N‐Dimethylformamide
as a Reagent 214