Emerging Fluorinated Motifs, 2 Volume Set

Synthesis, Properties and Applications

Inbunden, Engelska, 2020

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Beskrivning

A must-have resource for all the researchers working in the organofluorine and related fields This timely two-volume set uniquely focuses on emerging fluorinated motifs beyond R-CF3 and R-F, like R-CF2H, R-OCF3, R-SCF3 and R-SF5. It also offers descriptions of the properties, synthesis, and applications of these emerging fluorinated motifs in order to help readers design new chemical entities, while providing new interest for researchers in organofluorine chemistry and new tools for those in other areas. Emerging Fluorinated Motifs: Synthesis, Properties and Applications begins with a description of carbon-linked fluorine-containing groups that include monofluoromethyl and difluoromethyl groups. It then details combinations of heteroatoms, Oxygen, Sulfur, Selenium, Nitrogen, and Phosphorus with fluorine-containing groups, outlining subsections of the most popular current motifs. Fluoroalkyl ethers, thioethers, and the recent blossoming of the SF5 unit is covered. Other chapters look at: selenium-linked fluorine-containing motifs; construction of N?CF2H, N?CF3, N?CH2CF3 motifs; and the synthesis and applications of P¿Rf-containing molecules. -Focuses on the synthesis, properties, and applications of emerging fluorinated motifs -Covers carbon-linked fluorine-containing motifs, oxygen-linked fluorine-containing motifs, sulfur-linked fluorine-containing motifs, and more -Appeals to academic and industrial researchers working in organic chemistry, medicinal chemistry, food chemistry, and materials science -Edited by world-renowned experts in organofluorine chemistry Emerging Fluorinated Motifs is intended for academic research institutes, university libraries, researchers, graduate students, postdoctors, and researchers in the chemical industry.

Produktinformation

Utgivningsdatum:2020-05-20
Mått:178 x 252 x 48 mm
Vikt:1 973 g
Format:Inbunden
Språk:Engelska
Antal sidor:872
Förlag:Wiley-VCH Verlag GmbH
ISBN:9783527346813

Utforska kategorier

Biologi inom Naturvetenskap och teknik

Mer om författaren

Dominique Cahard, PhD, is Director of Research at the French National Center for Scientific Research, CNRS. His current research interests concern innovative methodologies for asymmetric synthesis of fluorinated molecules and the synthesis of fluorinated biomolecules. Jun-An Ma, PhD, is a Full Professor of organic chemistry at Tianjin University, P. R. of China. His current research efforts are focused on organofluorine chemistry, catalytic asymmetric synthesis, and the rational design & construction of biological molecules.

Innehållsförteckning

Preface xiiiVolume 1Part I Carbon©\Linked Fluorine©\Containing Motifs 11 Difluoromethylation and Difluoroalkylation of (Hetero)Arenes: Access to Ar(Het)–CF2H and Ar(Het)–CF2R 3Yu©\Lan Xiao and Xingang Zhang1.1 Introduction 31.2 Difluoromethylation of (Hetero)aromatics 31.2.1 Transition©\Metal©\Mediated/Catalyzed Nucleophilic Difluoromethylation of (Hetero)aromatics 31.2.2 Catalytic Metal©\Difluorocarbene©\Involved Coupling (MeDIC) Reaction 101.2.3 Transition©\Metal©\Catalyzed Radical Difluoromethylation of (Hetero)aryl Metals/Halides and Beyond 111.2.4 Radical C©¤H Bond Difluoromethylation of (Hetero)aromatics 191.3 Difluoroalkylation of Aromatics 221.3.1 Transition©\Metal©\Catalyzed Phosphonyldifluoromethylation of (Hetero)aromatics 231.3.2 Transition©\Metal©\Catalyzed Difluoroacetylation of (Hetero)aromatics and Beyond 261.3.3 Other Catalytic Difluoroalkylations of (Hetero)aromatics 371.4 Outlook 39References 422 Difluoromethylation and Difluoroalkylation of Aliphatic Unsaturated C=C, C≡C, and −N=C Bonds 47Sebastian Barata©\Vallejo and Al Postigo2.1 Introduction 472.2 Difluoromethylation of C¨TC Double Bonds 492.2.1 Intermolecular Difunctionalization of C¨TC Double Bonds 562.2.1.1 By Means of BrCF2P(O)(OR)2 562.2.1.2 By Means of Ph3P+CF2CO2− 592.2.1.3 By Means of HCF2R (R = CO2H, SO2NHNHBoc) 622.2.1.4 By Means of Selectfluor 652.2.1.5 By Means of BrCF2CO2Et 662.2.2 Difluoromethylation of C¨TC Double Bonds and Subsequent Cyclization 692.2.3 Difluoromethylation of C¨TC Double Bonds with Rearrangements 732.3 Difluoromethylation of Isocyanides 762.4 Difluoromethylation of Alkynes 792.5 Conclusion and Perspectives 82References 853 Difluoromethylation and Difluoroalkylation in C(sp3) Centers and C¨TO, C¨TC, and C¨TN Bonds 89Qiqiang Xie and Jinbo Hu3.1 Nucleophilic Difluoromethylation and Difluoroalkylation 893.1.1 By Means of XCF2PO(OEt)2 893.1.2 By Means of BrCF2CO2Et and BrCF2CH¨TCH2 893.1.3 By Means of Difluoromethylcadmium, Difluoromethylcopper, and Difluoromethylzinc Reagents 903.1.4 By Means of Difluoroalkylated Sulfone Reagents (XCF2SO2Ar) and Difluoromethylated Sulfoxides 903.1.5 By Means of Difluoroalkylated Silanes and Trifluoromethylsilane Reagents 943.1.6 By Means of Difluoromethyl Sulfoximine Reagent 963.1.7 Miscellaneous Reagents 963.2 Electrophilic Difluoromethylation and Difluoroalkylation 973.2.1 By Means of Difluorocarbene Reagents 973.2.2 By Means of CF3X (X ¨T H, I, TMS) Reagents 993.2.3 By Means of I(III)–CF2SO2Ph Reagent 1003.2.4 By Means of S©\((Phenylsulfonyl)difluoromethyl)thiophenium Salts 1003.3 Free Radical Difluoromethylation and Difluoroalkylation 1013.3.1 By Means of Iododifluoroacetates 1013.3.2 By Means of CF2Br2, CF2BrCl, or TMSCF2Br 1023.3.3 By Means of Phosphorus©\containing Reagents 1033.3.4 By Means of BrCF2CO2Et 1043.3.5 By Means of Halodifluoroketone or ©\Amide 1073.3.6 By Means of HCF2I and PhCH2CF2I 1073.3.7 By Means of HCF2SO2Cl and HCF2SO2Na or Zn(SO2CF2H)2 1083.3.8 By Means of Difluoromethylated Sulfones, Sulfoximines, Thioethers, and Sulfonium Salts 1093.3.9 By Means of TMSCF2CO2Et and ArCF2CO2H 112References 1124 Monofluoromethylation Reactions of Aliphatic Substrates and (Hetero)Arenes 119Qiqiang Xie and Jinbo Hu4.1 Nucleophilic Monofluoromethylation 1194.1.1 By Means of Fluoromalonates 1194.1.2 By Means of Fluoromethyl Phenyl Sulfone 1194.1.3 By Means of Fluorobis(phenylsulfonyl)methane 1214.1.4 By Means of 2©\Fluoro©\2©\Sulfonylketone 1224.1.5 By Means of 2©\Fluoro©\1,3©\benzodithiole©\1,1,3,3©\tetraoxide (FBDT) 1234.1.6 By Means of TMSCF(SO2Ph)2 (TFBSM) 1234.1.7 By Means of PhSO(NTBS)CH2F 1234.1.8 By Means of CH2FI 1244.1.9 By Means of Monofluoromethyl Phosphonium Salts 1244.2 Electrophilic Monofluoromethylation 1254.2.1 By Means of CH2FX (X = Cl, Br, I, OTf, OTs, OMs) 1254.2.2 By Means of S©\(monofluoromethyl)diarylsulfonium Tetrafluoroborate 1254.2.3 By Means of Monofluoromethylsulfoxinium Salts 1264.2.4 By Means of Monofluoromethylsulfonium Ylides 1274.2.5 By Means of Monofluoromethyl Phosphonium Salts 1274.3 Free Radical Monofluoromethylation 1284.3.1 By Means of (PhSO22CFI 1284.3.2 By Means of (H2FCSO2)2Zn (MFMS) 1284.3.3 By Means of CH2FSO2Cl 1284.3.4 By Means of PhSO(NTs)CH2F 1294.3.5 By Means of Monofluoromethyl Sulfone 1304.4 Transition©\Metal©\Catalyzed/Mediated Monofluoromethylation 1304.4.1 By Means of CH2FI 1304.4.2 By Means of PhSO2CHFI 1314.4.3 By Means of CH2FBr 1314.4.4 By Means of PTSO2CH2F 132References 1325 Synthesis of gem©\Difluorocyclopropanes 135Dmitriy M. Volochnyuk and Oleksandr O. Grygorenko5.1 Introduction 1355.2 Intramolecular Wurtz (Freund) Reaction 1405.3 Nucleophilic Fluorination of Pre©\existing Ring System 1405.4 Cyclopropanation of 1,1©\Difluoroalkenes 1425.5 Difluorocyclopropanation of Alkenes and Alkynes 1435.5.1 Fragmentation of Trihalomethyl Anions CF2X− (X = Cl, Br) 1455.5.2 Reduction of CF2Br2 with Zn or Other Reductants 1465.5.3 Decarboxylative Difluorocarbene Generation 1495.5.4 Difluorocarbene Generation by Nucleophilic Cleavage of a Carbene Precursor 1535.5.5 Decomposition of CF3©\substituted Organometallic Derivatives 1645.5.6 Lewis Base©\promoted Cleavage of the Ruppert–Prakash©\type Reagents XCF2SiMe3 (X = F, Cl, Br) 1695.5.7 Photodissociation of Difluorodiazirine 1825.5.8 Thermal Decomposition of Hexafluoropropene Oxide 1835.6 Michael©\induced Ring Closure (MIRC) 1835.7 Reactions at the Double Bond of gem©\Difluorocyclopropenes 1855.8 Conclusions 187References 187Part II Oxygen©\Linked Fluorine©\Containing Motifs 1956 Indirect Construction of the OCF3 Motif 197Pingping Tang and Xiaohuan Jiang6.1 Introduction 1976.2 Fluorination of Trichloromethyl Ethers 1976.3 Deoxyfluorination of Fluoroformates 1986.4 Oxidative Fluorodesulfurization 1986.5 Decarboxylative Fluorination 1996.6 Direct Trifluoromethylation 2006.7 Intramolecular OCF3 Migration 202References 2047 Reagents for Direct Trifluoromethoxylation 207Pingping Tang and Xiaohuan Jiang7.1 Introduction 2077.2 Trifluoromethyl Hypofluorite (FTM) 2077.3 Chloroxytrifluoromethane 2097.4 Bistrifluoromethyl Peroxide (BTMP) 2107.5 Bis(trifluoromethyl) Trioxide 2107.6 N©\Trifluoromethoxy Benzimidazole 2117.7 N©\Trifluoromethoxypyridinium 2137.8 N©\Trifluoromethoxy Triazolium Salts 2147.9 Trifluoromethyl Trifluoromethanesulfonate (TFMT) 2157.10 Organometallic Trifluoromethoxides 2177.11 Perfluoroalkylsulfurane 2197.12 Perfluoroalkylsulfurane Oxide 2197.13 2,4©\Dinitro(trifluoromethoxy)benzene (DNTFB) 2217.14 Trifluoromethyl Sulfonates (TFMS) 2217.15 Trifluoromethyl Benzoate (TFBz) 222References 2238 Direct Trifluoromethoxylation of Aromatics and Heteroaromatics 225Johnny W. Lee, Katarzyna N. Lee, and Ming©\Yu Ngai8.1 Introduction 2258.2 Direct Anionic Trifluoromethoxylation 2268.3 Direct Radical Trifluoromethoxylation 2398.4 Conclusion and Future Perspective 249References 2499 Direct Trifluoromethoxylation of Aliphatic Compounds 251Chaohuang Chen and Guosheng Liu9.1 Direct Trifluoromethoxylation of Alkenes 2519.1.1 Radical Trifluoromethoxylation of Alkenes 2519.1.2 Pd(II)©\Catalyzed Oxidative Trifluoromethoxylation of Alkenes 2529.1.3 Silver(I)©\catalyzed Trifluoromethoxylation of Alkenes 2559.1.4 Direct Trifluoromethoxylation at sp3Carbon Atoms 2589.1.4.1 Trifluoromethoxylation of Alkyl Halides and Alkyl Triflates 2589.1.4.2 Trifluoromethoxylation of Alkyl Alcohols and Alkyl Silanes 2599.1.4.3 Trifluoromethoxylation of C–H Bonds 2609.1.4.4 Nucleophilic Trifluoromethoxylation of Epoxides 2629.2 Trifluoromethoxylation of α©\Diazo Esters 2639.3 Summary and Outlook 264References 26510 Extension to the Construction of ORf Motifs (OCF2H, OCFH2, OCH2CF3, OCFHCH3) 267Jin©\Hong Lin and Ji©\Chang Xiao10.1 Introduction 26710.2 Construction of the OCF2H Group 26910.2.1 Insertion of Difluorocarbene into O©¤H Bond 26910.2.2 Decarboxylative Fluorination 27210.2.3 Direct Electrophilic Difluoromethylation 27210.2.4 Difluoromethoxylation 27310.2.5 Nucleophilic Fluorination 27410.3 Construction of the OCFH2 Group 27510.3.1 Monofluoromethylation 27510.3.2 Fluorination 27810.4 Construction of the OCH2CF3 Group 28010.4.1 Trifluoroethoxylation 28110.4.2 Trifluoroethylation 28310.5 Construction of the OCFHCH3 Group 28510.6 Conclusions and Perspectives 285References 285Volume 2Preface xviiPart III Sulfur©\Linked Fluorine©\Containing Motifs 28911 Indirect Trifluoromethylthiolation Methods 291Xiu©\Hua Xu and Feng©\Ling Qing12 Reagents for Direct Trifluoromethylthiolation 309He Liu, Hangming Ge, and Qilong Shen13 Trifluoromethylthiolation of Aromatic and Heteroaromatic Compounds 343Wenbin Yi, Zhidong Song, Jie Liu, Yasir Mumtaz, and Wei Zhang14 Synthesis of Trifluoromethylthiolated Alkenes and Alkynes 373Matthew N. Hopkinson15 Direct Trifluoromethylthiolation Toward C(sp3)–SCF3 Compounds 403Yumeng Liang, Dominique Cahard, and Norio Shibata16 Extension to the SCF2H, SCH2F, and SCF2R Motifs (R = PO(OEt)2, CO2R, Rf) 449Tatiana Besset and Thomas Poisson17 Synthesis and Applications of Fluorinated Sulfoxides (RSORF) and Sulfones (RSO2RF) 477Vinayak Krishnamurti, Colby Barrett, and G.K. Surya Prakash18 Pentafluorosulfanylation of Aromatics and Heteroaromatics 551Petr Beier19 Pentafluorosulfanylation of Aliphatic Substrates 571Günter Haufe20 Extension to SF4CF3 and SF4FG Groups 611Peer Kirsch21 Properties and Applications of Sulfur(VI) Fluorides 621Nicholas D. Ball22 Construction of S–RF Sulfilimines and S–RF Sulfoximines 675Emmanuel MagnierPart IV Selenium©\Linked Fluorine©\Containing Motifs 69123 When Fluorine Meets Selenium 693Thierry Billard and Fabien ToulgoatPart V Nitrogen©\Linked Fluorine©\Containing Motifs 72324 Construction of N©\CF2H, N©\CF3, and N©\CH2CF3 Motifs 725Thierry Milcent and Benoit CroussePart VI Phosphorus©\Linked Fluorine©\Containing Motifs 76325 Synthesis and Applications of P–Rf ©\Containing Molecules 765Fa©\Guang Zhang and Jun©\An MaIndex 809