Formaldehyde surrogates in multicomponent reactions

• Cecilia I. Attorresi,
• Javier A. Ramírez and
• Bernhard Westermann

Beilstein J. Org. Chem. 2025, 21, 564–595, doi:10.3762/bjoc.21.45

• this case, the mechanism appears to proceed through the formation of free radical species, where APS plays the role of oxidant and radical activator of DMSO, generating reactive radical species of DMSO or dimethyl sulfone that react with the nitrogen of saccharine compound 19 without the need for a

Photomechanochemistry: harnessing mechanical forces to enhance photochemical reactions

• Francesco Mele,
• Ana M. Constantin,
• Andrea Porcheddu,
• Raimondo Maggi,
• Giovanni Maestri,
• Nicola Della Ca’ and
• Luca Capaldo

Beilstein J. Org. Chem. 2025, 21, 458–472, doi:10.3762/bjoc.21.33

• (12.3, 0.2 mmol), tosyl chloride (12.4, 2 equiv), and tris(4-methoxyphenyl)amine (10 mol %) was milled in the presence of 100 wt % of SAOED at 30 Hz for 3 h, sulfone 12.5 was obtained in 89% yield after isolation. The synthesis of 12.5 was scaled up to 15 mmol scale, obtaining the desired product in a

Synthesis of new condensed naphthoquinone, pyran and pyrimidine furancarboxylates

• Kirill A. Gomonov,
• Vasilii V. Pelipko,
• Igor A. Litvinov,
• Ilya A. Pilipenko,
• Anna M. Stepanova,
• Nikolai A. Lapatin,
• Ruslan I. Baichurin and
• Sergei V. Makarenko

Beilstein J. Org. Chem. 2025, 21, 340–347, doi:10.3762/bjoc.21.24

• furopyran, furocoumarin [9][10], and furopyrimidine series [11][12]. It is known that the main approaches to the synthesis of naphtho[2,3-b]furan-4,9-diones are reactions of hydroxynaphthalene-1,4-dione with ethane-1,2-diol [13], chloroacetaldehyde [14], ethenyl methyl sulfone [15], or ethenyl acetate [16

Synthesis of disulfides and 3-sulfenylchromones from sodium sulfinates catalyzed by TBAI

• Zhenlei Zhang,
• Ying Wang,
• Xingxing Pan,
• Manqi Zhang,
• Wei Zhao,
• Meng Li and
• Hao Zhang

Beilstein J. Org. Chem. 2025, 21, 253–261, doi:10.3762/bjoc.21.17

• which the thiosulfonate was cleaved and then dimerized to form the disulfide. The reaction of sodium p-toluenesulfinate and styrene resulted in the generation of the corresponding vinyl sulfone (Scheme 5, reaction 2), suggesting the formation of p-toluenesulfonyl iodide during the reaction [50][51

Advances in the use of metal-free tetrapyrrolic macrocycles as catalysts

• Mandeep K. Chahal

Beilstein J. Org. Chem. 2024, 20, 3085–3112, doi:10.3762/bjoc.20.257

• different electronic properties (18, 25–41, Figure 6) were screened as catalysts for the sulfa-Michael addition of tert-butyl benzylmercaptan 42 to phenyl vinyl sulfone (43). Without the addition of a porphyrin, no product was formed. Among the non-alkylated porphyrins (18, 25–32) only the ones containing

Advances in radical peroxidation with hydroperoxides

• Oleg V. Bityukov,
• Pavel Yu. Serdyuchenko,
• Andrey S. Kirillov,
• Gennady I. Nikishin,
• Vera A. Vil’ and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2024, 20, 2959–3006, doi:10.3762/bjoc.20.249

Copper-catalyzed yne-allylic substitutions: concept and recent developments

• Shuang Yang and
• Xinqiang Fang

Beilstein J. Org. Chem. 2024, 20, 2739–2775, doi:10.3762/bjoc.20.232

• ). Further control experiments and DFT calculations show that during the catalytic process, tertiary amine directly participates as a nucleophilic reagent to give the ammonium salt, which then releases dimethylaminium to provide the final product (Scheme 12). Chiral allylic sulfone compounds can be easily

• -, stereo-, and enantioselectivities, resulting in a series of chiral yne-allylic sulfone compounds with different substituents (Scheme 13, 14a–q). Due to the high steric hindrance of the γ-site, nucleophilic substitutions preferentially occur at the α-site. Through subsequent control experiments, they

O,S,Se-containing Biginelli products based on cyclic β-ketosulfone and their postfunctionalization

• Kateryna V. Dil and
• Vitalii A. Palchykov

Beilstein J. Org. Chem. 2024, 20, 2143–2151, doi:10.3762/bjoc.20.184

• obtained products are characterized by the following signals: aromatic ring protons (6.25–8.23 ppm), Ar–CH group proton singlet (5.13–5.44 ppm), broadened NH singlets (7.78–10.89 ppm), as well as the corresponding signals of successive 3 × CH2 groups of the sulfone fragment (2.18–3.34 ppm). Such a set of

Regioselective quinazoline C2 modifications through the azide–tetrazole tautomeric equilibrium

• Dāgs Dāvis Līpiņš,
• Andris Jeminejs,
• Una Ušacka,
• Anatoly Mishnev,
• Māris Turks and
• Irina Novosjolova

Beilstein J. Org. Chem. 2024, 20, 675–683, doi:10.3762/bjoc.20.61

• substrates, but the step sulfoxide → sulfone was entirely slower and required stirring overnight (except for 8d (R = iC3H7)). With 2-chloro-6,7-dimethoxy-4-sulfonylquinazolines 8 in hand, we started to explore the reactivity in SNAr reactions (Scheme 5). Sulfonyl group dance reactions did not work in

Green and sustainable approaches for the Friedel–Crafts reaction between aldehydes and indoles

• Periklis X. Kolagkis,
• Eirini M. Galathri and
• Christoforos G. Kokotos

Beilstein J. Org. Chem. 2024, 20, 379–426, doi:10.3762/bjoc.20.36

Synthesis of π-conjugated polycyclic compounds by late-stage extrusion of chalcogen fragments

• Aissam Okba,
• Pablo Simón Marqués,
• Kyohei Matsuo,
• Naoki Aratani,
• Hiroko Yamada,
• Gwénaël Rapenne and
• Claire Kammerer

Beilstein J. Org. Chem. 2024, 20, 287–305, doi:10.3762/bjoc.20.30

• , were synthesized as direct soluble precursors of PBIs 6a,b, along with the corresponding oxides, namely sulfoxides 4a,b and sulfone 5 (Scheme 4). An X-ray crystal structure of the extended thiepine 3b confirmed its bent structure, with a protrusion of the sulfur atom out of the π-surface (Figure 1). As

• perylene moiety was next tested upon different stimuli, such as electron injection, thermal activation and photoirradiation. Importantly, the dinaphthothiepine S,S-dioxide, i.e., the sulfone soluble precursor 5, failed to deliver PBI whatever the activation mode (Scheme 4, bottom). For dinaphthothiepine 3

• selective oxidation of thiepine and selenepine to give rise to the corresponding sulfoxide 29b, selenoxide 29c and sulfone 30b in excellent yields. All the prepared chalcogen-doped HBC derivatives exhibit good solubility in organic solvents, in line with their highly distorted saddle-shaped or helical

Using the phospha-Michael reaction for making phosphonium phenolate zwitterions

• Matthias R. Steiner,
• Max Schmallegger,
• Larissa Donner,
• Johann A. Hlina,
• Christoph Marschner,
• Judith Baumgartner and
• Christian Slugovc

Beilstein J. Org. Chem. 2024, 20, 41–51, doi:10.3762/bjoc.20.6

• University of Technology, Stremayrgasse 9, 8010 Graz, Austria 10.3762/bjoc.20.6 Abstract The reactions of 2,4-di-tert-butyl-6-(diphenylphosphino)phenol and various Michael acceptors (acrylonitrile, acrylamide, methyl vinyl ketone, several acrylates, methyl vinyl sulfone) yield the respective phosphonium

• carbanion [13][14]. Also with other Michael acceptors such as methyl vinyl ketone, several acrylates as well as methyl vinyl sulfone the reaction proceeds smoothly under the same reaction conditions (Scheme 1). Conversions of 1 are usually quantitative within 24 h and all phosphonium phenolates can be

Anion–π catalysis on carbon allotropes

• M. Ángeles Gutiérrez López,
• Mei-Ling Tan,
• Giacomo Renno,
• Augustina Jozeliūnaitė,
• J. Jonathan Nué-Martinez,
• Javier Lopez-Andarias,
• Naomi Sakai and
• Stefan Matile

Beilstein J. Org. Chem. 2023, 19, 1881–1894, doi:10.3762/bjoc.19.140

• below that of unsubstituted NDIs despite stronger π acidity. Supported by experimental and computational data, this poor performance of dyad 46 was explained by lone-pair π interactions of the fullerene with the donating oxygens. These lone-pair π interactions were even more impactful on the sulfone

Radical chemistry in polymer science: an overview and recent advances

• Zixiao Wang,
• Feichen Cui,
• Yang Sui and
• Jiajun Yan

Beilstein J. Org. Chem. 2023, 19, 1580–1603, doi:10.3762/bjoc.19.116

• by radical unzipping depolymerization under photon or β-irradiation (Scheme 20a). Similarly, poly(olefin sulfone) undergoes depolymerization upon irradiation of light or electron beams [193][194]. It is an alternating copolymer of 1-olefins and SO2, and therefore the decomposition products are mostly

• gaseous [195]. While the depolymerization in both systems has a thermodynamic origin [196], the mechanism of poly(olefin sulfone) depolymerization is much more complex. Bowmer et al. proposed a simultaneous radical/cationic process (Scheme 20b) [197]. Meanwhile, an anionic process is also possible in the

• using benzophenone. Depolymerization mechanism of common photoresists. (a) A possible mechanism of radiation decomposition of poly(methyl methacrylate). (b) A proposed mechanism of simultaneous radical/cationic decomposition of poly(olefin sulfone) upon radiation [197]. Proposed mechanisms of

Synthesis of ether lipids: natural compounds and analogues

• Marco Antônio G. B. Gomes,
• Alicia Bauduin,
• Chloé Le Roux,
• Romain Fouinneteau,
• Wilfried Berthe,
• Mathieu Berchel,
• Hélène Couthon and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2023, 19, 1299–1369, doi:10.3762/bjoc.19.96

• has similar cell toxicity than edelfosine-C18 on HL-60 leukemic cells [129][130]. The authors also reported that the sulfone 26.5 (Figure 26B) had similar cytotoxicity than edelfosine-C18. In 1987, the group of E. J. Modest reported that the thioether 26.4 featured comparable cytotoxicity than C18

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

• in only 20% conversion after 60 minutes. Salts Both LiCl and NaCl induced a strong rate acceleration, resulting in (near) full conversion within only 20 minutes (Figure 1B). With LiCl the selectivity was maintained while the presence of NaCl leads to a decrease in selectivity due to sulfone formation

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

Photoredox catalysis enabling decarboxylative radical cyclization of γ,γ-dimethylallyltryptophan (DMAT) derivatives: formal synthesis of 6,7-secoagroclavine

• Alessio Regni,
• Francesca Bartoccini and
• Giovanni Piersanti

Beilstein J. Org. Chem. 2023, 19, 918–927, doi:10.3762/bjoc.19.70

• formation and a hydroxyl radical (•OH). However, it is possible to transform an alcohol into a leaving group, in the radical sense, by converting it into a halide or pseudohalide derivative [104][105]. For alcohol 8, all attempts to make a better leaving group, including phenyl sulfone derivative, to have

Construction of hexabenzocoronene-based chiral nanographenes

• Ranran Li,
• Di Wang,
• Shengtao Li and
• Peng An

Beilstein J. Org. Chem. 2023, 19, 736–751, doi:10.3762/bjoc.19.54

• this [7]helicene family by introducing different linkers such as nitrogen, sulfur, sulfone, ketone, methylene, and derivatives of ketone [44]. Due to the varied nature of the different linkers, the photophysical and semiconductor properties can be effectively tuned. Feng and co-workers reported a

Enolates ambushed – asymmetric tandem conjugate addition and subsequent enolate trapping with conventional and less traditional electrophiles

• Péter Kisszékelyi and
• Radovan Šebesta

Beilstein J. Org. Chem. 2023, 19, 593–634, doi:10.3762/bjoc.19.44

• , we have investigated the domino reaction of the formed metal enolates with activated alkenes 91 [59]. Alkenes with two activating groups were needed for efficient enolate-trapping reactions, sulfone or phosphonate activating groups being the most suitable ones (Scheme 23). Harutyunyan and co-workers

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

• and Technology Alliance (BRTA), Paseo de Miramón 194, 20014, Donostia San Sebastián, Spain Basque Fdn Sci, Ikerbasque, 48013 Bilbao, Spain 10.3762/bjoc.19.42 Abstract A light-driven metal-free protocol for the synthesis of sulfone-containing indoles under mild conditions is reported. Specifically

• halogen-bonded EDA complex (Ia) between the sulfone 2a and DABCO (Figure 4). When irradiated, this photoactive aggregate led to the formation of reactive alkyl radicals (IIa), which may react with indole 1a eventually yielding the product 3a through a classical HAS pathway [31][32][33]. Then, we

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

• corresponding sulfoxide and the sulfone was possible and the corresponding products were obtained in 98% and 95% yields, respectively. This reaction was successfully expanded to the trifluoromethylthiolation of derivatives bearing various directing groups such as substituted pyridines (4 examples, up to 84

• approach. Of high interest, the modularity of the SCF2CO2Et was highlighted by its conversion into various other fluorinated residues (amide, carboxylic acid) and its selective oxidation into the corresponding sulfoxide and sulfone. I.5) Trifluoromethylselenolation of aromatic and vinylic C(sp2)–H bonds by

Combretastatins D series and analogues: from isolation, synthetic challenges and biological activities

• Jorge de Lima Neto and
• Paulo Henrique Menezes

Beilstein J. Org. Chem. 2023, 19, 399–427, doi:10.3762/bjoc.19.31

• synthesis of combretastatin D-1 (1) using the flash vacuum pyrolysis (FVP) technique, which consisted on the contraction of 16-membered sulfone derivatives, by extrusion of sulfur dioxide [58]. The synthesis of the required sulfone was initiated by a Horner–Wadsworth–Emmons reaction between the aldehyde 52

• sulfone 134 using m-CPBA [63] followed by contraction of the macrocyclic ring by extrusion of SO2 using FVP gave compound 28 together with macrocycle 135, obtained from the simultaneous extrusion of SO2 and CO2. Cleavage of the methyl ether in 28 gave the desired product 2 in 0.6% overall yield after 10

• macrocyclization using SO3·pyridine [68] gave the corresponding thioether 151, which was oxidized to the cyclic sulfone 152 using m-CPBA. Extrusion of SO2 by FVP followed by demethylation of the formed macrolide furnished the compound 154 which can be converted in combretastatin D-1 (1) by known methodologies [43

Redox-active molecules as organocatalysts for selective oxidative transformations – an unperceived organocatalysis field

• Elena R. Lopat’eva,
• Igor B. Krylov,
• Dmitry A. Lapshin and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2022, 18, 1672–1695, doi:10.3762/bjoc.18.179

• that hydrogen bonding is considered as one of the key factors determining the selectivity of catalyst-free sulfoxidations [68]. In such reactions, the selectivity of sulfide oxidation by oxone (sulfoxide/sulfone ratio) was controlled by the solvent nature (deeper oxidation was observed in water than in

B–N/B–H Transborylation: borane-catalysed nitrile hydroboration

• Filip Meger,
• Alexander C. W. Kwok,
• Franziska Gilch,
• Dominic R. Willcox,
• Alex J. Hendy,
• Kieran Nicholson,
• Andrew D. Bage,
• Thomas Langer,
• Thomas A. Hunt and
• Stephen P. Thomas

Beilstein J. Org. Chem. 2022, 18, 1332–1337, doi:10.3762/bjoc.18.138

• relies upon stoichiometric reagents or transition-metal catalysis. Herein, a borane-catalysed hydroboration of nitriles to give primary amines is reported. Good yields (48–95%) and chemoselectivity (e.g., ester, nitro, sulfone) were observed. DFT calculations and mechanistic studies support the proposal

• %), nitro (1r, 67%), and sulfone (1s, 48%). The 1H NMR spectra of the crude reaction mixtures displayed no reduction of these functional groups. Such functional group tolerance was not exhibited by the other non-metal and boron-based catalytic nitrile hydroboration systems [22][23][24][27]. It should be