Emerging Fluorinated Motifs Synthesis, Properties, and Applications Volume 1&2

841 Pages·2020·26.772 MB·English

by  Dominique Cahard(eds.),  Jun‐An Ma(eds.)

Emerging Fluorinated Motifs
Emerging Fluorinated Motifs
Synthesis, Properties, and Applications
Volume 1
Edited by
Dominique Cahard
Jun‐An Ma
Editors All books published by Wiley‐VCH are carefully
produced. Nevertheless, authors, editors, and
Dr. Dominique Cahard
publisher do not warrant the information
CNRS ‐ UMR 6014 COBRA contained in these books, including this book,
University of Rouen Normandy to be free of errors. Readers are advised to keep
76821 Mont‐Saint‐Aignan in mind that statements, data, illustrations,
France procedural details or other items may
inadvertently be inaccurate.
Prof. Jun‐An Ma
Tianjin University Library of Congress Card No.: applied for
Department of Chemistry
300072 Tianjin British Library Cataloguing‐in‐Publication Data
China
A catalogue record for this book is available
from the British Library.
Cover Images:
Fluorine symbol © antonel adrian tudor/Alamy
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the Deutsche Nationalbibliothek
3d Silver Sphere © Rashevskyi Viacheslav/
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Abstract background © FotoMak/Getty Images
Nationalbibliografie; detailed bibliographic
data are available on the Internet
at <http://dnb.d‐nb.de>.
© 2020 Wiley‐VCH Verlag GmbH & Co. KGaA,
Boschstr. 12, 69469 Weinheim, Germany
All rights reserved (including those of
translation into other languages). No part of
this book may be reproduced in any form – by
photoprinting, microfilm, or any other
means – nor transmitted or translated into a
machine language without written permission
from the publishers. Registered names,
trademarks, etc. used in this book, even when
not specifically marked as such, are not to be
considered unprotected by law.
Print ISBN: 978‐3‐527‐34681‐3
ePDF ISBN: 978‐3‐527‐82432‐8
ePub ISBN: 978‐3‐527‐82433‐5
oBook ISBN: 978‐3‐527‐82434‐2
Typesetting SPi Global, Chennai, India
Printing and Binding
Printed on acid‐free paper
10 9 8 7 6 5 4 3 2 1
Emerging Fluorinated Motifs
Synthesis, Properties, and Applications
Volume 2
Edited by
Jun‐An Ma
Dominique Cahard
Editors All books published by Wiley‐VCH are carefully
produced. Nevertheless, authors, editors, and
Prof. Jun‐An Ma
publisher do not warrant the information
Tianjin University contained in these books, including this book,
Department of Chemistry to be free of errors. Readers are advised to keep
300072 Tianjin in mind that statements, data, illustrations,
China procedural details or other items may
inadvertently be inaccurate.
Dr. Dominique Cahard
CNRS ‐ UMR 6014 COBRA Library of Congress Card No.: applied for
University of Rouen Normandy
76821 Mont‐Saint‐Aignan British Library Cataloguing‐in‐Publication Data
France
A catalogue record for this book is available
from the British Library.
Cover Images:
Fluorine symbol © antonel adrian tudor/ Alamy
Bibliographic information published by
Stock Photo
the Deutsche Nationalbibliothek
3d Silver Sphere © Rashevskyi Viacheslav/
The Deutsche Nationalbibliothek
Shutterstock
lists this publication in the Deutsche
Abstract background © FotoMak/Getty Images
Nationalbibliografie; detailed bibliographic
data are available on the Internet
at <http://dnb.d‐nb.de>.
© 2020 Wiley‐VCH Verlag GmbH & Co. KGaA,
Boschstr. 12, 69469 Weinheim, Germany
All rights reserved (including those of
translation into other languages). No part of
this book may be reproduced in any form – by
photoprinting, microfilm, or any other
means – nor transmitted or translated into a
machine language without written permission
from the publishers. Registered names,
trademarks, etc. used in this book, even when
not specifically marked as such, are not to be
considered unprotected by law.
Print ISBN: 978‐3‐527‐34681‐3
ePDF ISBN: 978‐3‐527‐82432‐8
ePub ISBN: 978‐3‐527‐82433‐5
oBook ISBN: 978‐3‐527‐82434‐2
Typesetting SPi Global, Chennai, India
Printing and Binding
Printed on acid‐free paper
10 9 8 7 6 5 4 3 2 1
v
Contents
Preface xiii
Volume 1
Part I Carbon‐Linked Fluorine‐Containing Motifs 1
1 Difluoromethylation and Difluoroalkylation of (Hetero)Arenes: Access
to Ar(Het)–CF2H and Ar(Het)–CF2R 3
Yu‐Lan Xiao and Xingang Zhang
1.1 Introduction 3
1.2 Difluoromethylation of (Hetero)aromatics 3
1.2.1 Transition‐Metal‐Mediated/Catalyzed Nucleophilic
Difluoromethylation of (Hetero)aromatics 3
1.2.2 Catalytic Metal‐Difluorocarbene‐Involved Coupling (MeDIC)
Reaction 10
1.2.3 Transition‐Metal‐Catalyzed Radical Difluoromethylation of
(Hetero)aryl Metals/Halides and Beyond 11
1.2.4 Radical C─H Bond Difluoromethylation of (Hetero)aromatics 19
1.3 Difluoroalkylation of Aromatics 22
1.3.1 Transition‐Metal‐Catalyzed Phosphonyldifluoromethylation
of (Hetero)aromatics 23
1.3.2 Transition‐Metal‐Catalyzed Difluoroacetylation of (Hetero)aromatics
and Beyond 26
1.3.3 Other Catalytic Difluoroalkylations of (Hetero)aromatics 37
1.4 Outlook 39
References 42
2 Difluoromethylation and Difluoroalkylation of Aliphatic Unsaturated
C=C, C≡C, and −N=C Bonds 47
Sebastian Barata‐Vallejo and Al Postigo
2.1 Introduction 47
2.2 Difluoromethylation of C═C Double Bonds 49
2.2.1 Intermolecular Difunctionalization of C═C
Double Bonds 56
vi Contents
2.2.1.1 By Means of BrCF P(O)(OR) 56
2 2
2.2.1.2 By Means of Ph P+CF CO − 59
3 2 2
2.2.1.3 By Means of HCF R (R = CO H, SO NHNHBoc) 62
2 2 2
2.2.1.4 By Means of Selectfluor 65
2.2.1.5 By Means of BrCF CO Et 66
2 2
2.2.2 Difluoromethylation of C═C Double Bonds and Subsequent
Cyclization 69
2.2.3 Difluoromethylation of C═C Double Bonds
with Rearrangements 73
2.3 Difluoromethylation of Isocyanides 76
2.4 Difluoromethylation of Alkynes 79
2.5 Conclusion and Perspectives 82
References 85
3 Difluoromethylation and Difluoroalkylation in C(sp3) Centers and C═O,
C═C, and C═N Bonds 89
Qiqiang Xie and Jinbo Hu
3.1 Nucleophilic Difluoromethylation and Difluoroalkylation 89
3.1.1 By Means of XCF PO(OEt) 89
2 2
3.1.2 By Means of BrCF CO Et and BrCF CH═CH 89
2 2 2 2
3.1.3 By Means of Difluoromethylcadmium, Difluoromethylcopper,
and Difluoromethylzinc Reagents 90
3.1.4 By Means of Difluoroalkylated Sulfone Reagents (XCF SO Ar) and
2 2
Difluoromethylated Sulfoxides 90
3.1.5 By Means of Difluoroalkylated Silanes and Trifluoromethylsilane
Reagents 94
3.1.6 By Means of Difluoromethyl Sulfoximine Reagent 96
3.1.7 Miscellaneous Reagents 96
3.2 Electrophilic Difluoromethylation and Difluoroalkylation 97
3.2.1 By Means of Difluorocarbene Reagents 97
3.2.2 By Means of CF X (X ═ H, I, TMS) Reagents 99
3
3.2.3 By Means of I(III)–CF SO Ph Reagent 100
2 2
3.2.4 By Means of S‐((Phenylsulfonyl)difluoromethyl)thiophenium Salts 100
3.3 Free Radical Difluoromethylation and Difluoroalkylation 101
3.3.1 By Means of Iododifluoroacetates 101
3.3.2 By Means of CF Br , CF BrCl, or TMSCF Br 102
2 2 2 2
3.3.3 By Means of Phosphorus‐containing
Reagents 103
3.3.4 By Means of BrCF CO Et 104
2 2
3.3.5 By Means of Halodifluoroketone or ‐Amide 107
3.3.6 By Means of HCF I and PhCH CF I 107
2 2 2
3.3.7 By Means of HCF SO Cl and HCF SO Na or Zn(SO CF H) 108
2 2 2 2 2 2 2
3.3.8 By Means of Difluoromethylated Sulfones, Sulfoximines, Thioethers,
and Sulfonium Salts 109
3.3.9 By Means of TMSCF CO Et and ArCF CO H 112
2 2 2 2
References 112
Contents vii
4 Monofluoromethylation Reactions of Aliphatic Substrates
and (Hetero)Arenes 119
Qiqiang Xie and Jinbo Hu
4.1 Nucleophilic Monofluoromethylation 119
4.1.1 By Means of Fluoromalonates 119
4.1.2 By Means of Fluoromethyl Phenyl Sulfone 119
4.1.3 By Means of Fluorobis(phenylsulfonyl)methane 121
4.1.4 By Means of 2‐Fluoro‐2‐Sulfonylketone 122
4.1.5 By Means of 2‐Fluoro‐1,3‐benzodithiole‐1,1,3,3‐tetraoxide
(FBDT) 123
4.1.6 By Means of TMSCF(SO Ph) (TFBSM) 123
2 2
4.1.7 By Means of PhSO(NTBS)CH F 123
2
4.1.8 By Means of CH FI 124
2
4.1.9 By Means of Monofluoromethyl Phosphonium Salts 124
4.2 Electrophilic Monofluoromethylation 125
4.2.1 By Means of CH FX (X = Cl, Br, I, OTf, OTs, OMs) 125
2
4.2.2 By Means of S‐(monofluoromethyl)diarylsulfonium
Tetrafluoroborate 125
4.2.3 By Means of Monofluoromethylsulfoxinium Salts 126
4.2.4 By Means of Monofluoromethylsulfonium Ylides 127
4.2.5 By Means of Monofluoromethyl Phosphonium Salts 127
4.3 Free Radical Monofluoromethylation 128
4.3.1 By Means of (PhSO ) CFI 128
2 2
4.3.2 By Means of (H FCSO ) Zn (MFMS) 128
2 2 2
4.3.3 By Means of CH FSO Cl 128
2 2
4.3.4 By Means of PhSO(NTs)CH F 129
2
4.3.5 By Means of Monofluoromethyl Sulfone 130
4.4 Transition‐Metal‐Catalyzed/Mediated Monofluoromethylation 130
4.4.1 By Means of CH FI 130
2
4.4.2 By Means of PhSO CHFI 131
2
4.4.3 By Means of CH FBr 131
2
4.4.4 By Means of PTSO CH F 132
2 2
References 132
5 Synthesis of gem‐Difluorocyclopropanes 135
Dmitriy M. Volochnyuk and Oleksandr O. Grygorenko
5.1 Introduction 135
5.2 Intramolecular Wurtz (Freund) Reaction 140
5.3 Nucleophilic Fluorination of Pre‐existing Ring System 140
5.4 Cyclopropanation of 1,1‐Difluoroalkenes 142
5.5 Difluorocyclopropanation of Alkenes and Alkynes 143
5.5.1 Fragmentation of Trihalomethyl Anions CF X− (X = Cl, Br) 145
2
5.5.2 Reduction of CF Br with Zn or Other Reductants 146
2 2
5.5.3 Decarboxylative Difluorocarbene Generation 149
5.5.4 Difluorocarbene Generation by Nucleophilic Cleavage of a Carbene
Precursor 153
viii Contents
5.5.5 Decomposition of CF ‐substituted Organometallic
3
Derivatives 164
5.5.6 Lewis Base‐promoted Cleavage of the Ruppert–Prakash‐type
Reagents XCF SiMe (X = F, Cl, Br) 169
2 3
5.5.7 Photodissociation of Difluorodiazirine 182
5.5.8 Thermal Decomposition of Hexafluoropropene Oxide 183
5.6 Michael‐induced Ring Closure (MIRC) 183
5.7 Reactions at the Double Bond of gem‐Difluorocyclopropenes 185
5.8 Conclusions 187
References 187
Part II Oxygen‐Linked Fluorine‐Containing Motifs 195
6 Indirect Construction of the OCF3 Motif 197
Pingping Tang and Xiaohuan Jiang
6.1 Introduction 197
6.2 Fluorination of Trichloromethyl Ethers 197
6.3 Deoxyfluorination of Fluoroformates 198
6.4 Oxidative Fluorodesulfurization 198
6.5 Decarboxylative Fluorination 199
6.6 Direct Trifluoromethylation 200
6.7 Intramolecular OCF Migration 202
3
References 204
7 Reagents for Direct Trifluoromethoxylation 207
Pingping Tang and Xiaohuan Jiang
7.1 Introduction 207
7.2 Trifluoromethyl Hypofluorite (FTM) 207
7.3 Chloroxytrifluoromethane 209
7.4 Bistrifluoromethyl Peroxide (BTMP) 210
7.5 Bis(trifluoromethyl) Trioxide 210
7.6 N‐Trifluoromethoxy Benzimidazole 211
7.7 N‐Trifluoromethoxypyridinium 213
7.8 N‐Trifluoromethoxy Triazolium Salts 214
7.9 Trifluoromethyl Trifluoromethanesulfonate (TFMT) 215
7.10 Organometallic Trifluoromethoxides 217
7.11 Perfluoroalkylsulfurane 219
7.12 Perfluoroalkylsulfurane Oxide 219
7.13 2,4‐Dinitro(trifluoromethoxy)benzene (DNTFB) 221
7.14 Trifluoromethyl Sulfonates (TFMS) 221
7.15 Trifluoromethyl Benzoate (TFBz) 222
References 223