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

• Fei Wang Lingchun Li Chuanfa Ni Jinbo Hu Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Ling-Ling Road, Shanghai 200032, China 10.3762/bjoc.10.32 Abstract Background: 1,1-Difluoroalkenes cannot only be used as valuable

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

• Xueliang Jiang Feng-Ling Qing Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, 2999 North Renmin Lu, Shanghai

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

• microreactor technology to overcome long-standing problems in synthetic organofluorine chemistry are showcased. Reactions using hazardous fluorinating reagents Direct fluorination employing elemental fluorine (F2) is one of the most straightforward methods to make fluorine-containing molecules with high atom

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

• inspection of the medicinal chemistry literature will reveal two obvious themes in the structures of current drug candidates: the ubiquity of nitrogen heterocycles, and the popularity of organofluorine moieties. Therefore, it seems natural that a combination of these two features will offer rich

• from fluorine-containing organic building blocks. Such an approach benefits from the wide variety, and frequently the low cost, of today’s commercially available organofluorine molecules [63][64]. For example, the fluorinated aziridines 2 and 3 presented earlier (Figure 1) were synthesised through a

Copper-catalyzed trifluoromethylation of alkenes with an electrophilic trifluoromethylating reagent

• Xiao-Ping Wang,
• Jin-Hong Lin,
• Cheng-Pan Zhang,
• Ji-Chang Xiao and
• Xing Zheng

Beilstein J. Org. Chem. 2013, 9, 2635–2640, doi:10.3762/bjoc.9.299

• Xiao-Ping Wang Jin-Hong Lin Cheng-Pan Zhang Ji-Chang Xiao Xing Zheng Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,345 Lingling Road, Shanghai 200032, China Institute of Pharmacy and Pharmacology, University of South China

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

• be observed [1][2][3][4][5][6]. As a consequence, organofluorine chemistry has become an integral part of pharmaceutical [6][7][8][9][10][11][12][13][14][15][16] and agrochemical research [16][17][18][19][20]. About 20% of all pharmaceuticals and roughly 40% of agrochemicals are fluorinated

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

Triol-promoted activation of C–F bonds: Amination of benzylic fluorides under highly concentrated conditions mediated by 1,1,1-tris(hydroxymethyl)propane

• Pier Alexandre Champagne,
• Alexandre Saint-Martin,
• Mélina Drouin and
• Jean-François Paquin

Beilstein J. Org. Chem. 2013, 9, 2451–2456, doi:10.3762/bjoc.9.283

• under highly concentrated conditions, where solvents cannot interfere with the interaction between the organofluorine compound and the triol. Various benzylic fluorides react with secondary amines or anilines to form benzylic amines in good yields. Keywords: C–F bond activation; highly concentrated

• conditions; nucleophilic substitution; hydrogen bond; organofluorine; triol; Introduction The discovery of mild methods for the activation of C–F bonds is of high importance both from a fundamental point of view as well as for potential practical applications [1]. Specifically for aliphatic monofluorides, a

Asymmetric allylic alkylation of Morita–Baylis–Hillman carbonates with α-fluoro-β-keto esters

• Lin Yan,
• Zhiqiang Han,
• Bo Zhu,
• Caiyun Yang,
• Choon-Hong Tan and
• Zhiyong Jiang

Beilstein J. Org. Chem. 2013, 9, 1853–1857, doi:10.3762/bjoc.9.216

• properties, compared with their parent compounds [1]. Due to the rareness of organofluorine compounds in nature, synthetic fluorinated compounds have been widely applied in numerous areas, including materials, agrochemicals, pharmaceuticals and fine chemicals [2][3][4]. In this context, the stereoselective

Recyclable fluorous cinchona alkaloid ester as a chiral promoter for asymmetric fluorination of β-ketoesters

• Wen-Bin Yi,
• Xin Huang,
• Zijuan Zhang,
• Dian-Rong Zhu,
• Chun Cai and
• Wei Zhang

Beilstein J. Org. Chem. 2012, 8, 1233–1240, doi:10.3762/bjoc.8.138

• compounds have unique properties because fluorine forms a strong carbon–fluorine bond with a small covalent radius and high electronegativity. Other than fluorinated polymers in materials science, organofluorine compounds have gained increasing popularity in medical chemistry and agricultural chemistry

• organofluorine chemistry plays an important role in the life sciences [3][4]. A fluorine atom has been introduced to the α-position of some biologically interesting β-ketoesters, such as erythromycin and sesquiterpenic drimane (Figure 1) [5][6]. The achiral fluorination of β-ketoesters can be achieved by

Conformational analysis, stereoelectronic interactions and NMR properties of 2-fluorobicyclo[2.2.1]heptan-7-ols

• Fátima M. P. de Rezende,
• Marilua A. Moreira,
• Rodrigo A. Cormanich and
• Matheus P. Freitas

Beilstein J. Org. Chem. 2012, 8, 1227–1232, doi:10.3762/bjoc.8.137

• as reactivity of a wide range of chemical and biological systems [1]. However, it has been argued that organic fluorine hardly ever participates in HB, due to the poor proton acceptor ability of the fluorine atom [2]; nevertheless, there are some instances of organofluorine compounds forming seven

• atom (θ = 330.0°) is the most stable structure in the gas phase (this structure will be further referred to as the global minimum). This suggests that a F∙∙∙HO intramolecular HB is operating and governs the stability of 5; however, different organofluorine compounds with similar orientation of the

• 1hJF,OH SSCC in this aliphatic organofluorine compound, and is the main factor responsible for the large value of 1hJF,OH in the global minimum. Some organofluorine compounds and the 2-fluorobicyclo[2.2.1]heptan-7-ols (5–8) theoretically studied in this work. Potential energy surfaces for the

Single enantiomer synthesis of α-(trifluoromethyl)-β-lactam

• Václav Jurčík,
• Alexandra M. Z. Slawin and
• David O'Hagan

Beilstein J. Org. Chem. 2011, 7, 759–766, doi:10.3762/bjoc.7.86

• ; organofluorine building blocks; α-(trifluoromethyl)-β-lactam; Introduction β-Lactams (azetidin-2-ones) have played a prominent role in medicinal chemistry and many structural variants have been prepared and elaborated [1]. Similarly, the CF3 group is an ubiquitous substituent in pharmaceutical research, where

Aromatic and heterocyclic perfluoroalkyl sulfides. Methods of preparation

• Vladimir N. Boiko

Beilstein J. Org. Chem. 2010, 6, 880–921, doi:10.3762/bjoc.6.88

• -process; perfluoroalkylation; perfluoroalkyl sulfides; SRF-introduction; Review 1. Introduction Perfluoroalkyl sulfides of aromatic and heterocyclic compounds have been an important aspect in the general development of organofluorine chemistry over the last twenty years. Alkyl aryl sulfides containing

Synthesis and crystallographic analysis of meso-2,3-difluoro-1,4-butanediol and meso-1,4-dibenzyloxy-2,3-difluorobutane

• Bruno Linclau,
• Leo Leung,
• Jean Nonnenmacher and
• Graham Tizzard

Beilstein J. Org. Chem. 2010, 6, No. 62, doi:10.3762/bjoc.6.62

• ; epoxide opening; gauche effect; organofluorine; vicinal difluoride; Introduction Selective fluorination of bioactive compounds is a widely employed strategy for the modification of their properties [1]. Fluorine atoms can be introduced to modulate the pKa of adjacent acidic and basic functional groups as

The C–F bond as a conformational tool in organic and biological chemistry

• Luke Hunter

Beilstein J. Org. Chem. 2010, 6, No. 38, doi:10.3762/bjoc.6.38

• Luke Hunter School of Chemistry, The University of Sydney, NSW 2006, Australia 10.3762/bjoc.6.38 Abstract Organofluorine compounds are widely used in many different applications, ranging from pharmaceuticals and agrochemicals to advanced materials and polymers. It has been recognised for many

• of functional molecules that exploit these conformational effects will then be presented, drawing from a diverse range of molecules including pharmaceuticals, organocatalysts, liquid crystals and peptides. Keywords: conformation; functional molecules; organofluorine chemistry; stereochemistry

• organofluorine molecule and these can be substantially stronger. For example, in α-fluoroamides (e.g. 3, Figure 1a) there is a strong preference for the C–F bond to align antiparallel to the C=O bond, a conformation in which the C–F dipole opposes the amide dipole. An analogous effect exists with other α

Synthesis of gem-difluoromethylenated analogues of boronolide

• Jing Lin,
• Xiao-Long Qiu and
• Feng-Ling Qing

Beilstein J. Org. Chem. 2010, 6, No. 37, doi:10.3762/bjoc.6.37

• Jing Lin Xiao-Long Qiu Feng-Ling Qing College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, 2999 North Renmin Lu, Shanghai 201620, China Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu

Looking forward to volume six

• Jonathan Clayden

Beilstein J. Org. Chem. 2010, 6, No. 1, doi:10.3762/bjoc.6.1

• way within the journal, these papers can be viewed together using the “thematic series” tool on the website. Recent series have covered the topical themes of flow chemistry [1], supramolecular chemistry [2] and liquid crystals [3], and further series on carbohydrate chemistry and on organofluorine

Reduction of arenediazonium salts by tetrakis(dimethylamino)ethylene (TDAE): Efficient formation of products derived from aryl radicals

• Mohan Mahesh,
• John A. Murphy,
• Franck LeStrat and
• Hans Peter Wessel

Beilstein J. Org. Chem. 2009, 5, No. 1, doi:10.3762/bjoc.5.1

• ][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51][52][53][54][55][56][57][58][59] to electron-poor aliphatic and benzylic halides, notably those derived from organofluorine sources. Burkholder, Dolbier and Médebielle reported [28] that the

Synthesis of deep- cavity fluorous calix[4]arenes as molecular recognition scaffolds

• Maksim Osipov,
• Qianli Chu,
• Steven J. Geib,
• Dennis P. Curran and
• Stephen G. Weber

Beilstein J. Org. Chem. 2008, 4, No. 36, doi:10.3762/bjoc.4.36

• ; organofluorine; (perfluoroalkyl)alkyl aryl ethers; Introduction Calixarenes [1] are one of the most useful types of macrocyclic scaffolds. Since first reported by Zinke and Ziegler [2], calix[4]arenes have been used for a variety of molecular recognition, nanotechnology, and supramolecular applications. These

Enantioselective nucleophilic difluoromethylation of aromatic aldehydes with Me₃SiCF₂SO₂Ph and PhSO₂CF₂H reagents catalyzed by chiral quaternary ammonium salts

• Chuanfa Ni,
• Fang Wang and
• Jinbo Hu

Beilstein J. Org. Chem. 2008, 4, No. 21, doi:10.3762/bjoc.4.21

• Chuanfa Ni Fang Wang Jinbo Hu Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, China 10.3762/bjoc.4.21 Abstract Background Although the nucleophilic difluoromethylation of aldehydes, ketones, and

• −, the fluorine substitution being commonly on the carbanion center) to an electrophile, represents one of the major methods for the synthesis of organofluorine compounds [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18]. In recent years, a few methods have been reported for the enantioselective

Understanding the mechanism of Pd-catalyzed allylic substitution of the cyclic difluorinated carbonates

• Jun Xu,
• Xiao-Long Qiu and
• Feng-Ling Qing

Beilstein J. Org. Chem. 2008, 4, No. 18, doi:10.3762/bjoc.4.18

• Jun Xu Xiao-Long Qiu Feng-Ling Qing Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, China College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, 2999 North Renmin Lu

Stereoselective α-fluoroamide and α-fluoro- γ-lactone synthesis by an asymmetric zwitterionic aza-Claisen rearrangement

• Kenny Tenza,
• Julian S. Northen,
• David O'Hagan and
• Alexandra M. Z. Slawin

Beilstein J. Org. Chem. 2005, 1, No. 13, doi:10.1186/1860-5397-1-13

• purity.[11] Successes in this area has advanced methodology in organofluorine chemistry considerably over the last decade or so.[1][2] In this paper we explore an alternative approach for the preparation of α-fluorocarbonyls using an asymmetric zwitterionic aza-Claisen rearrangement on appropriate