Beyond n-dopants for organic semiconductors: use of bibenzo[d]imidazoles in UV-promoted dehalogenation reactions of organic halides

• Kan Tang,
• Megan R. Brown,
• Chad Risko,
• Melissa K. Gish,
• Garry Rumbles,
• Phuc H. Pham,
• Oana R. Luca,
• Stephen Barlow and
• Seth R. Marder

Beilstein J. Org. Chem. 2023, 19, 1912–1922, doi:10.3762/bjoc.19.142

• synthesize by other methods, whereas aryl halides afford dehalogenated arenes. One example also demonstrates that the approach may have utility for selectively dehalogenating compounds containing different halogens. The photoacceleration of these reactions appears to occur through photocleavage of the dimers

Recent advancements in iodide/phosphine-mediated photoredox radical reactions

• Tinglan Liu,
• Yu Zhou,
• Junhong Tang and
• Chengming Wang

Beilstein J. Org. Chem. 2023, 19, 1785–1803, doi:10.3762/bjoc.19.131

• nitroarenes 48 (Scheme 22). The protocol demonstrated excellent tolerance towards a wide range of reducible functional groups, including halogens (such as chlorine, bromine, and even iodine), aldehydes, ketones, carboxyl groups, and cyano groups. Iodination Alkyl iodide is considered to be the most reactive

Exploring the role of halogen bonding in iodonium ylides: insights into unexpected reactivity and reaction control

• Carlee A. Montgomery and
• Graham K. Murphy

Beilstein J. Org. Chem. 2023, 19, 1171–1190, doi:10.3762/bjoc.19.86

• coined “halogen bonding” by Dumas et al. in 1978 [21][22], and only in 2013 did it receive an official IUPAC definition [23]. Iodine is the largest and most polarizable of the halogens, and as such it predominantly engages in halogen bonding (I > Br > Cl >> F) [24]. Halogen bonding was first observed by

• ][36][37][38][39]. This anisotropic electron distribution manifests itself in many ways, such as the L-shaped packing observed with diatomic halogens resulting from the secondary bonding between the positive end of one halogen and the negative end of another [40]. σ-Holes can be assessed both

Selective and scalable oxygenation of heteroatoms using the elements of nature: air, water, and light

• Damiano Diprima,
• Hannes Gemoets,
• Stefano Bonciolini and
• Koen Van Aken

Beilstein J. Org. Chem. 2023, 19, 1146–1154, doi:10.3762/bjoc.19.82

• oxygen- or radical-sensitive functionalities (i.e., an amino (2w) or nitro group (2x)). On the other hand, oxidizable groups, such as alcohols (2e), and halogens, such as such as chloro and fluoro on the aromatic ring (2i ,2j, 2k), were well tolerated. However, the presence of a iodo group (2v

Photoredox catalysis harvesting multiple photon or electrochemical energies

• Mattia Lepori,
• Simon Schmid and
• Joshua P. Barham

Beilstein J. Org. Chem. 2023, 19, 1055–1145, doi:10.3762/bjoc.19.81

Photocatalytic sequential C–H functionalization expediting acetoxymalonylation of imidazo heterocycles

• Deepak Singh,
• Shyamal Pramanik and
• Soumitra Maity

Beilstein J. Org. Chem. 2023, 19, 666–673, doi:10.3762/bjoc.19.48

• the aryl ring – as electron-releasing groups (Me, OMe) showed little more reactivity than electron-withdrawing groups (CN) at the same position (4b, 4f, and 4g). Halogen-substituted IPs also followed the general reactivity trend of the respective halogens (4c–e). Excellent reactivity was found for o-F

Direct C2–H alkylation of indoles driven by the photochemical activity of halogen-bonded complexes

• Martina Mamone,
• Giuseppe Gentile,
• Jacopo Dosso,
• Maurizio Prato and
• Giacomo Filippini

Beilstein J. Org. Chem. 2023, 19, 575–581, doi:10.3762/bjoc.19.42

• ). Mechanistic investigations are reported. These studies provide convincing evidences for the photochemical formation of reactive open-shell species. Keywords: alkylation; EDA complex; halogens; indoles; photochemistry; Findings Direct replacement of carbon–hydrogen (C–H) bonds with new carbon–carbon (C–C

Transition-metal-catalyzed C–H bond activation as a sustainable strategy for the synthesis of fluorinated molecules: an overview

• Louis Monsigny,
• Floriane Doche and
• Tatiana Besset

Beilstein J. Org. Chem. 2023, 19, 448–473, doi:10.3762/bjoc.19.35

• disulfide F3CS–SCF3 were employed (Scheme 2, 10 examples, up to 76% yield). With this approach, derivatives bearing an aromatic part substituted at the para-position with electron-donating substituents (1a,b), halogens (1c) as well as electron-withdrawing groups (1d) were difunctionalized in good yields

• trifluoromethylthiolation of azacalix[1]arene[3]pyridines by C–H bond activation using a complex of Cu(ClO4)2·6H2O and the shelf-stable Me4NSCF3 [115][116] as a nucleophilic source of SCF3 (Scheme 3) [100]. Within these conditions, a set of six azacalix[1]arene[3]pyridines bearing electron-donating groups, halogens or

• groups as well as halogens (16b–f, 62–91% yields). The meta-substituted (16f) and disubstituted (16j) products were obtained in high yields (73% and 79%, respectively). In 2018, Anbarasan and co-workers described a palladium-catalyzed trifluoromethylthiolation of arenes by C–H bond activation bearing

NaI/PPh₃-catalyzed visible-light-mediated decarboxylative radical cascade cyclization of N-arylacrylamides for the efficient synthesis of quaternary oxindoles

• Dan Liu,
• Yue Zhao and
• Frederic W. Patureau

Beilstein J. Org. Chem. 2023, 19, 57–65, doi:10.3762/bjoc.19.5

• in moderate to good yields (Scheme 2). Electron-donating groups at the para-position of the phenyl ring, such as methyl or methoxy groups, decreased slightly the yield, to 68% and 66%, respectively (3ba and 3ca). When these substituents were replaced by common halogens or electron-withdrawing groups

Synthesis of α-(perfluoroalkylsulfonyl)propiophenones: a new set of reagents for the light-mediated perfluoroalkylation of aromatics

• Durbis J. Castillo-Pazos,
• Juan D. Lasso and
• Chao-Jun Li

Beilstein J. Org. Chem. 2022, 18, 788–795, doi:10.3762/bjoc.18.79

• in yields of 64% and 20%, respectively. Arenes containing halogens were attempted; however, in accordance to previous reported literature, the compounds were found to decompose under the ultraviolet radiation necessary for the homolysis of the reagent [25]. Lastly, some heteroaromatic substrates such

Synthesis of piperidine and pyrrolidine derivatives by electroreductive cyclization of imine with terminal dihaloalkanes in a flow microreactor

• Yuki Naito,
• Naoki Shida and
• Mahito Atobe

Beilstein J. Org. Chem. 2022, 18, 350–359, doi:10.3762/bjoc.18.39

• anions of imine 1 with the terminal dihaloalkane is also considered to be an important factor in the formation of the desired product 3a. Therefore, a model reaction was conducted using dihaloalkanes with different types of terminal halogens (Cl, Br, and I) (Table 7). When the terminal halogen of the

A visible-light-induced, metal-free bis-arylation of 2,5-dichlorobenzoquinone

• Pieterjan Winant and
• Wim Dehaen

Beilstein J. Org. Chem. 2021, 17, 2315–2320, doi:10.3762/bjoc.17.149

• conditions, different anilines were applied to explore the scope of the reaction (Scheme 1). The procedure is tolerant towards a range of different substituents. Both 4- and 3-substituted anilines readily functionalized the quinone (3a–n), and the halogens and other functional groups present are providing

Halides as versatile anions in asymmetric anion-binding organocatalysis

• Lukas Schifferer,
• Martin Stinglhamer,
• Kirandeep Kaur and
• Olga García Macheño

Beilstein J. Org. Chem. 2021, 17, 2270–2286, doi:10.3762/bjoc.17.145

• the cationic reactive species. Keywords: anion binding; asymmetric catalysis; halide anions; hydrogen donors; noncovalent interactions; Introduction Halogens and the respective anionic halides occupy an essential role in natural and chemical processes [1][2][3][4]. While in chemical syntheses

• halogens are often regarded as surrogates for further functionalization, their role in natural and physiological processes is much more diverse. One of these processes is the ability of large complex molecules and enzymes to recognize halide anions via hydrogen bonds in aqueous media [5]. Amongst others

• anion-binding catalysis has been successfully demonstrated for other halogens, and different types of substrates such as the benzhydryl cation [48][49][50][51]. Halides as counter-anions vs nucleophiles The latest advances in anion-binding catalysis not only allowed for excellent translation of

On the application of 3d metals for C–H activation toward bioactive compounds: The key step for the synthesis of silver bullets

• Renato L. Carvalho,
• Amanda S. de Miranda,
• Mateus P. Nunes,
• Roberto S. Gomes,
• Guilherme A. M. Jardim and
• Eufrânio N. da Silva Júnior

Beilstein J. Org. Chem. 2021, 17, 1849–1938, doi:10.3762/bjoc.17.126

Double-headed nucleosides: Synthesis and applications

• Vineet Verma,
• Jyotirmoy Maity,
• Vipin K. Maikhuri,
• Ritika Sharma,
• Himal K. Ganguly and
• Ashok K. Prasad

Beilstein J. Org. Chem. 2021, 17, 1392–1439, doi:10.3762/bjoc.17.98

• attached directly to the sugar or via a linker. Further modifications were introduced by the substitution of some of the naturally occurring nucleobases by halogens or alkyl groups. On the other hand, a variety of heterocyclic/carbocyclic moieties were considered as the head of these modified nucleosides

Icilio Guareschi and his amazing “1897 reaction”

• Gian Cesare Tron,
• Alberto Minassi,
• Giovanni Sorba,
• Mara Fausone and
• Giovanni Appendino

Beilstein J. Org. Chem. 2021, 17, 1335–1351, doi:10.3762/bjoc.17.93

• bromine in the presence of other halogens [67]. The test is based on the action of sulfitic leucobases of triphenylmethane dyes, such the decolorized fuchsine (Schiff reagent), which develops a deep violet color in the presence of traces of bromine. The reaction is very sensitive and selective for bromine

• in the presence of other halogens. Using this test, Guareschi could demonstrate the presence of traces of bromide or brominated compounds in a variety of matrixes, including food and tissues (Supporting Information File 1, eighth paragraph). The paternity of this reaction was contested by the French

Structural effects of meso-halogenation on porphyrins

• Keith J. Flanagan,
• Maximilian Paradiz Dominguez,
• Zoi Melissari,
• Hans-Georg Eckhardt,
• René M. Williams,
• Dáire Gibbons,
• Caroline Prior,
• Gemma M. Locke,
• Alina Meindl,
• Aoife A. Ryan and
• Mathias O. Senge

Beilstein J. Org. Chem. 2021, 17, 1149–1170, doi:10.3762/bjoc.17.88

• , Trinity College Dublin, The University of Dublin, Dublin 2, Ireland Van ‘t Hoff Institute for Molecular Sciences, University of Amsterdam, P.O. Box 94157, 1090 GD Amsterdam, The Netherlands 10.3762/bjoc.17.88 Abstract The use of halogens in the crystal engineering of supramolecular porphyrin assemblies

• some cases can be undesirable. Recent studies from our group have been carried out on the use of halogens as a binding motif in cubanes [15], bicyclo[1.1.1]pentane [16], and nonplanar porphyrins [17]. Another reason to investigate the effect of meso-halogenation of porphyrins is due to the potential of

• induced distortion of the macrocyclic core. Due to their relatively large size and high electronegativity, halogens induce a conformational distortion of the porphyrin core that is significant compared to those induced by other substitution groups. As recently illustrated in a review by Kielmann and Senge

Valorisation of plastic waste via metal-catalysed depolymerisation

• Francesca Liguori,
• Carmen Moreno-Marrodán and
• Pierluigi Barbaro

Beilstein J. Org. Chem. 2021, 17, 589–621, doi:10.3762/bjoc.17.53

• to the action of chemical (acids, air, halogens, solvents) or physical agents (heat, light). For polymers, the properties involved are, for instance, tensile strength, colour or shape, the change of which is usually associated with a modification of the chemical composition (e.g., as a consequence of

Synthesis of (Z)-3-[amino(phenyl)methylidene]-1,3-dihydro-2H-indol-2-ones using an Eschenmoser coupling reaction

• Lukáš Marek,
• Lukáš Kolman,
• Jiří Váňa,
• Jan Svoboda and
• Jiří Hanusek

Beilstein J. Org. Chem. 2021, 17, 527–539, doi:10.3762/bjoc.17.47

• -thioiminium salt and the cleaved leaving group should be a poor nucleophile in order to suppress the reverse reaction. In most cases halogens (mainly Br and I) fulfill these criteria but for highly congested thioamides only triflates gave desirable yields [36]. Moreover, several new alternatives to the

The synthesis of chiral β-naphthyl-β-sulfanyl ketones via enantioselective sulfa-Michael reaction in the presence of a bifunctional cinchona/sulfonamide organocatalyst

• Deniz Tözendemir and
• Cihangir Tanyeli

Beilstein J. Org. Chem. 2021, 17, 494–503, doi:10.3762/bjoc.17.43

• this pattern was with the 3-methyl derivative of chalcone, which resulted in a small decrease in enantioselectivity (78% to 70% ee, entry 2 in Table 3 and Table 5) when THF was changed to DCM. For halogens and electron-withdrawing substituents, an opposite behavior was observed. The use of DCM instead

Synthesis of legonmycins A and B, C(7a)-hydroxylated bacterial pyrrolizidines

• Wilfred J. M. Lewis,
• David M. Shaw and
• Jeremy Robertson

Beilstein J. Org. Chem. 2021, 17, 334–342, doi:10.3762/bjoc.17.31

• , irrespective of the site of activation, the subsequent ejection of the activating reagent would generate an extended iminium ion whose capture by adventitious water would produce legonmycin A directly. For context, the treatment of enol esters with oxidizing agents to give α-hydroxyketones, or halogens to give

The preparation and properties of 1,1-difluorocyclopropane derivatives

• Kymbat S. Adekenova,
• Peter B. Wyatt and
• Sergazy M. Adekenov

Beilstein J. Org. Chem. 2021, 17, 245–272, doi:10.3762/bjoc.17.25

• )-fluorodienals 136 and 137 in high yields by a base-induced cleavage of the weak distal bond of gem-difluorocyclopropyl acetaldehydes 138 (Scheme 59) [109]. Xiao et al. studied the ring-opening reactions of difluoro(methylene)cyclopropane 139 with halogens and amines [110][111]. А number of fluorine-containing

Benzothiazolium salts as reagents for the deoxygenative perfluoroalkylthiolation of alcohols

• Armin Ariamajd,
• Nils J. Gerwien,
• Benjamin Schwabe,
• Stefan Dix and
• Matthew N. Hopkinson

Beilstein J. Org. Chem. 2021, 17, 83–88, doi:10.3762/bjoc.17.8

• corresponding (pentafluoroethyl) thioethers 3 in generally high yields (Scheme 4). A wide range of functional groups were tolerated, including the halogens Cl, Br, and I, thus opening the door for further functionalization of the products via cross-coupling. The propargylic alcohol substrate 2i could also be

Synthesis of novel fluorinated building blocks via halofluorination and related reactions

• Attila Márió Remete,
• Tamás T. Novák,
• Melinda Nonn,
• Matti Haukka,
• Ferenc Fülöp and
• Loránd Kiss

Beilstein J. Org. Chem. 2020, 16, 2562–2575, doi:10.3762/bjoc.16.208

• of halogens [19]. Halofluorinaton-related reactions, such as fluorosulfuration, fluoroselenation, nitrofluorination, and nitriminofluorination, in contrast, are much less studied [20]. Deoxyfluorination, that is fluorine introduction accompanied by oxygen removal (subtypes: OH→F exchange, C=O→CF2

• , the selective elimination of the former halogens was expected. Taking into account the stereochemical requirements of the E2 elimination (the halide group and the β-hydrogen atom should be antiperiplanar relative to each other), the limited availability of the compound (rac)-5b, and Bredt’s rule

When metal-catalyzed C–H functionalization meets visible-light photocatalysis

• Lucas Guillemard and
• Joanna Wencel-Delord

Beilstein J. Org. Chem. 2020, 16, 1754–1804, doi:10.3762/bjoc.16.147