Organo-fluorine chemistry V

• David O’Hagan

Beilstein J. Org. Chem. 2021, 17, 737–738, doi:10.3762/bjoc.17.63

• David O'Hagan School of Chemistry, Biomedical Sciences Research Complex, University of St Andrews, North Haugh, St Andrews, Fife KY16 9ST, United Kingdom 10.3762/bjoc.17.63 Keywords: Organo-fluorine chemistry; This is the fifth thematic issue on organo-fluorine chemistry in the Beilstein Journal

• Beilstein Journal of Organic Chemistry has become a settled home for papers in contemporary organo-fluorine chemistry. Authors have presented their recent findings or, in some cases, reviewed important areas, from bioactives to materials, and collectively the papers highlight the vibrancy and range of

• activity associated with this theme. Organo-fluorine chemistry merits our attention as an important discipline within contemporary organic chemistry contributing in a unique way to innovation and performance in the development of functional molecules. This issue will be historically memorable as all of the

Syntheses of fluorooxindole and 2-fluoro-2-arylacetic acid derivatives from diethyl 2-fluoromalonate ester

• Antal Harsanyi,
• Graham Sandford,
• Dmitri S. Yufit and
• Judith A.K. Howard

Beilstein J. Org. Chem. 2014, 10, 1213–1219, doi:10.3762/bjoc.10.119

• processes. Keywords: fluorinated building blocks; fluoroarylacetic acid; fluoromalonate; fluorooxindole; organo-fluorine; selective fluorination; Introduction Since 1954, when Fried and Sabo observed that the incorporation of a fluorine atom into a corticosteroid derivative led to valuable enhanced

A novel family of (1-aminoalkyl)(trifluoromethyl)- and -(difluoromethyl)phosphinic acids – analogues of α-amino acids

• Natalia V. Pavlenko,
• Tatiana I. Oos,
• Yurii L. Yagupolskii,
• Igor I. Gerus,
• Uwe Doeller and
• Lothar Willms

Beilstein J. Org. Chem. 2014, 10, 722–731, doi:10.3762/bjoc.10.66

• ; hydrophosphinylation; organo-fluorine; Shiff bases; (trifluoromethyl)phosphinic acid; Introduction For a long time aminophosphonic and aminophosphinic acids as isosters of aminocarboxylic acids have attracted a particular interest for the preparation of analogues of numerous natural products. Among the literature

Deoxygenative gem-difluoroolefination of carbonyl compounds with (chlorodifluoromethyl)trimethylsilane and triphenylphosphine

• Fei Wang,
• Lingchun Li,
• Chuanfa Ni and
• Jinbo Hu

Beilstein J. Org. Chem. 2014, 10, 344–351, doi:10.3762/bjoc.10.32

• . Conclusion: Similar to many other Wittig-type gem-difluoroolefination reactions in the presence of PPh3, the reaction of TMSCF2Cl with aldehydes and activated ketones is effective. Keywords: (chlorodifluoromethyl)trimethylsilane; difluorocarbene; gem-difluoroolefin; organo-fluorine; Wittig reaction; ylide

Organocatalytic asymmetric fluorination of α-chloroaldehydes involving kinetic resolution

• Kazutaka Shibatomi,
• Takuya Okimi,
• Yoshiyuki Abe,
• Akira Narayama,
• Nami Nakamura and
• Seiji Iwasa

Beilstein J. Org. Chem. 2014, 10, 323–331, doi:10.3762/bjoc.10.30

• catalysis; chlorination; fluorination; organocatalyst; organo-fluorine; Introduction Fluorinated organic molecules are of considerable interest in pharmaceutical and agricultural chemistry owing to the unique properties of the fluorine atom [1][2]. These compounds, especially with one or more fluorinated

The difluoromethylene (CF₂) group in aliphatic chains: Synthesis and conformational preference of palmitic acids and nonadecane containing CF₂ groups

• Yi Wang,
• Ricardo Callejo,
• Alexandra M. Z. Slawin and
• David O’Hagan

Beilstein J. Org. Chem. 2014, 10, 18–25, doi:10.3762/bjoc.10.4

• in the extended anti-zig-zag chain and suggests a design modification for long chain aliphatics which can introduce conformational stability. Keywords: difluoromethylene; fatty acids; fluorination; organic fluorine chemistry; organo-fluorine; palmitic acid; Introduction The selective replacement of

Synthesis, characterization and initial evaluation of 5-nitro-1-(trifluoromethyl)-3H-1λ³,2-benziodaoxol-3-one

• Nico Santschi,
• Roman C. Sarott,
• Elisabeth Otth,
• Reinhard Kissner and
• Antonio Togni

Beilstein J. Org. Chem. 2014, 10, 1–6, doi:10.3762/bjoc.10.1

• trifluoromethylation; 19F NMR kinetics; nitration; organo-fluorine; Introduction Since the advent of the hypervalent-iodine-based electrophilic trifluoromethylation reagents 1 and 2 in 2006 they have found widespread application in organic synthesis (Figure 1) [1][2][3][4]. Recently, increasing interest has been

Cu-Mediated trifluoromethylation of benzyl, allyl and propargyl methanesulfonates with TMSCF₃

• Xueliang Jiang and
• Feng-Ling Qing

Beilstein J. Org. Chem. 2013, 9, 2862–2865, doi:10.3762/bjoc.9.322

• ; methanesulfonates; organo-fluorine; trifluoromethylation; Introduction Fluorinated organic molecules are extremely important in agrochemicals, pharmaceuticals and materials [1][2][3][4][5][6]. In recent years, (trifluoroethyl)arenes have drawn increasing attention in medicinal chemistry and related fields [7][8][9

Modulating NHC catalysis with fluorine

• Yannick P. Rey and
• Ryan Gilmour

Beilstein J. Org. Chem. 2013, 9, 2812–2820, doi:10.3762/bjoc.9.316

• :13.0). Keywords: catalysis; enantioselectivity; fluorine; gauche effect; organo-fluorine; Steglich rearrangement; Introduction Molecular editing using fluorine is a powerful strategy to modulate the conformation and reactivity of small molecule organocatalysts [1][2][3]. The negligible steric penalty

Flow microreactor synthesis in organo-fluorine chemistry

• Hideki Amii,
• Aiichiro Nagaki and
• Jun-ichi Yoshida

Beilstein J. Org. Chem. 2013, 9, 2793–2802, doi:10.3762/bjoc.9.314

• 615-8510, Japan 10.3762/bjoc.9.314 Abstract Organo-fluorine compounds are the substances of considerable interest in various industrial fields due to their unique physical and chemical properties. Despite increased demand in wide fields of science, synthesis of fluoro-organic compounds is still often

• synthesis and reactions of fluorine-containing molecules by the use of flow microreactor systems to overcome long-standing problems in fluorine chemistry. Keywords: defluorination; fluorine; fluorination; flow microreactor; organo-fluorine; perfluoroalkylation; Review Fluorine is a key element in the

• gaining a significant importance in wide field of science and technology, and there have been the associated growing need for new and more efficient synthetic methods. As highlighted here, each of these elegant flow microreactor syntheses surely supplies the innovative methods for the synthesis of organo

Stereoselectively fluorinated N-heterocycles: a brief survey

• Xiang-Guo Hu and
• Luke Hunter

Beilstein J. Org. Chem. 2013, 9, 2696–2708, doi:10.3762/bjoc.9.306

• , their hydrogen bonding ability, and their basicity. Finally, some methods for the synthesis of stereoselectively fluorinated N-heterocycles will also be reviewed. Keywords: conformation; fluorine; N-heterocycles; iminosugars; medicinal chemistry; organo-fluorine; Review 1. Introduction A cursory

One-pot cross-enyne metathesis (CEYM)–Diels–Alder reaction of gem-difluoropropargylic alkynes

• Santos Fustero,
• Paula Bello,
• Javier Miró,
• María Sánchez-Roselló,
• Günter Haufe and
• Carlos del Pozo

Beilstein J. Org. Chem. 2013, 9, 2688–2695, doi:10.3762/bjoc.9.305

• group, which involved the use of 1,7-octadiene as an internal source of ethylene. Keywords: cross metathesis; Diels–Alder; one-pot reaction; organo-fluorine; propargylic difluorides; Introduction In recent years the number of applications of olefin metathesis as a mild and competitive synthetic method

Diastereoselectivity in the Staudinger reaction of pentafluorosulfanylaldimines and ketimines

• Alexander Penger,
• Cortney N. von Hahmann,
• Alexander S. Filatov and
• John T. Welch

Beilstein J. Org. Chem. 2013, 9, 2675–2680, doi:10.3762/bjoc.9.303

• control of the C–N ketimine geometry was reflected in the stereochemistry of the product β-lactam. Cyclization of imines with a stereogenic center bearing SF5 was reflected in the 1,2-lk,lk selectivity of the β-lactam. Keywords: aldimine; Cornforth transition state; diastereoselectivity; β-lactam; organo

• -fluorine; α-pentafluorosulfanyl aldehyde; Introduction The pentafluorosulfanyl (SF5) group is one of the few truly new functional groups to be introduced to synthetic organic chemistry in the last 100 years [1][2][3][4][5][6]. With pseudooctahedral geometry around sulfur, the SF5 group is a unique

Multigramme synthesis and asymmetric dihydroxylation of a 4-fluorobut-2E-enoate

• James A. B. Laurenson,
• John A. Parkinson,
• Jonathan M. Percy,
• Giuseppe Rinaudo and
• Ricard Roig

Beilstein J. Org. Chem. 2013, 9, 2660–2668, doi:10.3762/bjoc.9.301

• d-chloroform/diisopropyl tartrate showed distinct baseline separated signals for different enantiomers. Keywords: asymmetric; dihydroxylation; ee determination; fluorination; fluorosugars; organo-fluorine; Introduction Selective fluorination can be used to make subtle but decisive modifications of

Reaction of 2,2,4,4-tetrakis(trifluoromethyl)-1,3-dithiethane with N-vinyl compounds

• Viacheslav A. Petrov and
• Will Marshall

Beilstein J. Org. Chem. 2013, 9, 2615–2619, doi:10.3762/bjoc.9.295

• was confirmed by single crystal X-ray diffraction. Keywords: 1-(hexafluoroisopropyl)-3-vinyl-1,3-dihydro-2H-imidazole-2-thione; 2,2,4,4-terakis(trifluoromethyl)-1,3-dithiethane; 4-amino-2,2-bis(trifluoromethyl)thietanes; organo-fluorine; Introduction Hexafluorothioacetone (HFTA) and

Recent advances in transition metal-catalyzed Csp²-monofluoro-, difluoro-, perfluoromethylation and trifluoromethylthiolation

• Grégory Landelle,
• Armen Panossian,
• Sergiy Pazenok,
• Jean-Pierre Vors and
• Frédéric R. Leroux

Beilstein J. Org. Chem. 2013, 9, 2476–2536, doi:10.3762/bjoc.9.287

• ² carbon atoms. Transformations are discussed according to the reaction-type and the metal employed. The review will not extend to conventional non-transition metal methods to these fluorinated groups. Keywords: catalysis; cross-coupling; difluoromethylation; fluorine; monofluoromethylation; organo

• -fluorine; transition metal; trifluoromethylation; trifluoromethylthiolation; Review Introduction The incorporation of fluorine or fluorinated moieties into organic compounds plays a key role in Life-Science oriented research as often-profound changes of the physico-chemical and biological properties can

Consecutive cross-coupling reactions of 2,2-difluoro-1-iodoethenyl tosylate with boronic acids: efficient synthesis of 1,1-diaryl-2,2-difluoroethenes

• Ju Hee Kim,
• Su Jeong Choi and
• In Howa Jeong

Beilstein J. Org. Chem. 2013, 9, 2470–2475, doi:10.3762/bjoc.9.286

• -difluoro-1-iodoethenyl tosylate; organo-fluorine; Introduction The synthesis of 2,2-disubstituted-1,1-difluoroethenes have received much attention to synthetic organofluorine chemists in recent years because of their unique chemical reactivities toward nucleophiles to produce monofluorinated organic

Oxidative 3,3,3-trifluoropropylation of arylaldehydes

• Akari Ikeda,
• Masaaki Omote,
• Shiho Nomura,
• Miyuu Tanaka,
• Atsushi Tarui,
• Kazuyuki Sato and
• Akira Ando

Beilstein J. Org. Chem. 2013, 9, 2417–2421, doi:10.3762/bjoc.9.279

• reaction involves oxidative 3,3,3-trifluoropropylation of an arylaldehyde to afford 4,4,4-trifluoro-1-arylbutan-1-one. Keywords: cesium fluoride; organo-fluorine; 1,3-proton shift; trifluoromethyl; 3,3,3-trifluoropropenyl; Introduction Trifluoromethyl groups are an essential motif in pharmaceuticals

Cu-catalyzed trifluoromethylation of aryl iodides with trifluoromethylzinc reagent prepared in situ from trifluoromethyl iodide

• Yuzo Nakamura,
• Motohiro Fujiu,
• Tatsuya Murase,
• Yoshimitsu Itoh,
• Hiroki Serizawa,
• Kohsuke Aikawa and
• Koichi Mikami

Beilstein J. Org. Chem. 2013, 9, 2404–2409, doi:10.3762/bjoc.9.277

• . Keywords: organo-fluorine; Ruppert–Prakash reagent; trifluoromethyl; trifluoromethylation; trifluoromethyl zinc; Introduction Organo-fluorine compounds have received considerable attention in the fields of biomedical chemistry, agrochemistry, and organic material science due to their unique chemical

A one-pot synthesis of 3-trifluoromethyl-2-isoxazolines from trifluoromethyl aldoxime

• Raoni S. B. Gonçalves,
• Michael Dos Santos,
• Guillaume Bernadat,
• Danièle Bonnet-Delpon and
• Benoit Crousse

Beilstein J. Org. Chem. 2013, 9, 2387–2394, doi:10.3762/bjoc.9.275

• yield the corresponding trifluoromethylated γ-amino alcohols. Keywords: aldoxime; amino alcohol; fluorine; isoxazole; isoxazoline; organo-fluorine; Introduction 2-Isoxazolines are five-membered heterocyclic compounds that have been widely applied in medicinal and organic chemistry. This nucleus is

Crystal design using multipolar electrostatic interactions: A concept study for organic electronics

• Peer Kirsch,
• Qiong Tong and
• Harald Untenecker

Beilstein J. Org. Chem. 2013, 9, 2367–2373, doi:10.3762/bjoc.9.272

• isotropic charge transport compared to the “herring bone” stacking observed for other acenes. Keywords: aromatic stacking; charge carrier transport; crystal design; electrostatic control; organic semiconductor; organo-fluorine; Introduction Within a very few years the first organic semiconductors have

Direct electrophilic N-trifluoromethylthiolation of amines with trifluoromethanesulfenamide

• Sébastien Alazet,
• Kevin Ollivier and
• Thierry Billard

Beilstein J. Org. Chem. 2013, 9, 2354–2357, doi:10.3762/bjoc.9.270

• trifluoromethylsulfanylamines with good yields. Keywords: amine; fluorine; organo-fluorine; trifluoromethanesulfenamide; trifluoromethylsulfanylamine; trifluoromethylthiolation; Introduction In past decades, fluorinated molecules have found more and more applications in a variety of fields, especially in the design of new

Regioselective 1,4-trifluoromethylation of α,β-unsaturated ketones via a S-(trifluoromethyl)diphenylsulfonium salts/copper system

• Satoshi Okusu,
• Yutaka Sugita,
• Etsuko Tokunaga and
• Norio Shibata

Beilstein J. Org. Chem. 2013, 9, 2189–2193, doi:10.3762/bjoc.9.257

• yields. Keywords: 1,4-addition; copper; fluorine; Michael addition; organo-fluorine; trifluoromethylation; Introduction One of the challenges in synthetic organic chemistry is the nucleophilic 1,4-addition of the trifluoromethyl (CF3) group into electron-deficient internal alkenes as represented by the

Regioselective carbon–carbon bond formation of 5,5,5-trifluoro-1-phenylpent-3-en-1-yne

• Motoki Naka,
• Tomoko Kawasaki-Takasuka and
• Takashi Yamazaki

Beilstein J. Org. Chem. 2013, 9, 2182–2188, doi:10.3762/bjoc.9.256

• electrophiles, under equilibration of the possible two anionic species. Keywords: additives; computation; Li···F chelation; deprotonation; electron-withdrawing effect; organo-fluorine; Introduction We have previously reported [1] the interesting behavior of (E)-1-chloro-3,3,3-trifluoropropene ((E)-1) [2][3][4

Organo-fluorine chemistry III

• David O'Hagan

Beilstein J. Org. Chem. 2013, 9, 2180–2181, doi:10.3762/bjoc.9.255

• David O'Hagan School of Chemistry, University of St Andrews, Fife, KY16 9ST, United Kingdom 10.3762/bjoc.9.255 Keywords: organo-fluorine; It is a pleasure to introduce the 3rd in the series of Thematic Issues on organo-fluorine chemistry for the Beilstein Journal of Organic Chemistry (BJOC

• ). These series have become progressively more successful over time in terms of the number and quality of the contributions received. It is also pleasing to note that the profile and impact factor of the journal has increased steadily over this time as well. Organo-fluorine chemistry is enjoying a high

• contributions in the Thematic Series focus on this aspect of organo-fluorine chemistry. Fluorine touches all categories of performance compounds extending from bioactives to organic materials, and society demands continual improvements in the quality and performance of products and devices. As the global