On the photoluminescence in triarylmethyl-centered mono-, di-, and multiradicals

• Daniel Straub,
• Markus Gross,
• Mona E. Arnold,
• Julia Zolg and
• Alexander J. C. Kuehne

Beilstein J. Org. Chem. 2025, 21, 964–998, doi:10.3762/bjoc.21.80

• improved photostability (see Figure 1a). While the triaryl oxyether-TTM does not enhance the ϕ, triaryl thioether-TTM exhibits a ϕ of up to 37.5% (in cyclohexane). Due to the stronger electron donating effect of the chalcogens compared to halogens, the emission is shifted to lower energies with λem = 625

• nm for the triaryl oxyether-TTM and λem = 655 nm for the triaryl thioether-TTM (in dichloromethane (DCM)) [44]. The stronger bathochromic shift and the loss of vibrational features in the photoluminescence spectrum point towards a CT excited state in the triaryl thioether-TTM, which could explain the

Origami with small molecules: exploiting the C–F bond as a conformational tool

• Patrick Ryan,
• Ramsha Iftikhar and
• Luke Hunter

Beilstein J. Org. Chem. 2025, 21, 680–716, doi:10.3762/bjoc.21.54

Sequential two-step, one-pot microwave-assisted Urech synthesis of 5-monosubstituted hydantoins from L-amino acids in water

• Wei-Jin Chang,
• Sook Yee Liew,
• Thomas Kurz and
• Siow-Ping Tan

Beilstein J. Org. Chem. 2025, 21, 596–600, doi:10.3762/bjoc.21.46

• conversion of the thioether-containing methionine to hydantoin (H2j) was obtained with a moderate yield of 59%. Lastly, no hydantoin product was observed by 1H NMR when cysteine was subject to the one-pot procedure, possibly due to disulfide formation of the highly nucleophilic thiol group of the cysteine

Direct trifluoroethylation of carbonyl sulfoxonium ylides using hypervalent iodine compounds

• Radell Echemendía,
• Carlee A. Montgomery,
• Fabio Cuzzucoli,
• Antonio C. B. Burtoloso and
• Graham K. Murphy

Beilstein J. Org. Chem. 2024, 20, 3182–3190, doi:10.3762/bjoc.20.263

• [28]. In 2017, the Aϊssa group described a procedure to better synthesize such α-alkyl-substituted carbonyl sulfoxonium ylides [29]. This protocol involved the alkylation of a dialkyl thioether, counterion exchange, oxidation, and eventual acylation (Scheme 1a). More recently, the Burtoloso group

Recent advances in transition-metal-free arylation reactions involving hypervalent iodine salts

• Ritu Mamgain,
• Kokila Sakthivel and
• Fateh V. Singh

Beilstein J. Org. Chem. 2024, 20, 2891–2920, doi:10.3762/bjoc.20.243

• ) [91]. This method manifests the synthesis of stable thioether-linked synthetic conjugates 93 and 96 displaying its efficacy via the alteration of the affibody zEGFR and the histone protein H2A. The procedure involved synthesizing the diaryliodonium salt and appraising the proficiency of oxime ligation

Synthesis, electrochemical properties, and antioxidant activity of sterically hindered catechols with 1,3,4-oxadiazole, 1,2,4-triazole, thiazole or pyridine fragments

• Daria A. Burmistrova,
• Andrey Galustyan,
• Nadezhda P. Pomortseva,
• Kristina D. Pashaeva,
• Maxim V. Arsenyev,
• Oleg P. Demidov,
• Mikhail A. Kiskin,
• Andrey I. Poddel’sky,
• Nadezhda T. Berberova and
• Ivan V. Smolyaninov

Beilstein J. Org. Chem. 2024, 20, 2378–2391, doi:10.3762/bjoc.20.202

• (simeprevir, ritonavir, cobicistat), and other types of biological activities [15][16][17][18][19]. Besides, among the registered sulfur-containing drugs, 19% contain a thiazole ring, and 15% contain a thioether group [20]. Oxadiazole fragments are found in the structures of anticancer drugs (zibotentan

• view of studying their potential biological activity. This work aimed to obtain new multifunctional catechols containing pharmacologically active heterocyclic fragments such as thiazole, 1,3,4-oxadiazole, 1,2,4-triazole, and pyridine. We decided to use a non-hydrolyzable thioether group as a bridging

• changes. This is confirmed by the appearance of an absorption maximum in the UV–visible spectrum at λ = 490 nm, which is characteristic of thiolated o-benzoquinones. This absorption band corresponds to intramolecular charge transfer between the thioether group and the o-benzoquinone fragment [36][62][63

From perfluoroalkyl aryl sulfoxides to ortho thioethers

• Yang Li,
• Guillaume Dagousset,
• Emmanuel Magnier and
• Bruce Pégot

Beilstein J. Org. Chem. 2024, 20, 2108–2113, doi:10.3762/bjoc.20.181

• Yang Li Guillaume Dagousset Emmanuel Magnier Bruce Pegot Université Paris-Saclay, UVSQ, CNRS, UMR 8180, Institut Lavoisier de Versailles, 78035 Versailles Cedex, France 10.3762/bjoc.20.181 Abstract Access to original ortho thioether derivatives was achieved through a [3,3]-rearrangement in a one

Discovery of antimicrobial peptides clostrisin and cellulosin from Clostridium: insights into their structures, co-localized biosynthetic gene clusters, and antibiotic activity

• Moisés Alejandro Alejo Hernandez,
• Katia Pamela Villavicencio Sánchez,
• Rosendo Sánchez Morales,
• Karla Georgina Hernández-Magro Gil,
• David Silverio Moreno-Gutiérrez,
• Eddie Guillermo Sanchez-Rueda,
• Yanet Teresa-Cruz,
• Brian Choi,
• Armando Hernández Garcia,
• Alba Romero-Rodríguez,
• Oscar Juárez,
• Siseth Martínez-Caballero,
• Mario Figueroa and
• Corina-Diana Ceapă

Beilstein J. Org. Chem. 2024, 20, 1800–1816, doi:10.3762/bjoc.20.159

• resulting peptides exhibit unique structural features due to thioether bridges between dehydrated serine or threonine (Dha/Dhb) and cysteine (Cys). These thioether bridges lead to cyclic peptides with the modified amino acid lanthionine (Dha-Cys) or methyllanthionine (Dhb-Cys). The strong antimicrobial

• activity of nisin, a lanthipeptide produced by certain strains of Lactococcus lactis, is dependent on thioether-ring formation [14]. Additional post-translational modifications contributing to their distinct biological activities were identified [15][16]. Intermolecular disulfide bridges were proved to

• times dehydrated was identified. Cyclization reactions introduced thioether cross-links between dehydrated Thr/Ser residues and specific cysteine thiol groups. However, due to identical masses of dehydrated linear peptides (lacking thioether rings) and cyclic forms (containing Dhb and Dha rings), a

Enhancing structural diversity of terpenoids by multisubstrate terpene synthases

• Min Li and
• Hui Tao

Beilstein J. Org. Chem. 2024, 20, 959–972, doi:10.3762/bjoc.20.86

• synthase (CLS) from Cannabis sativa and 5-epi-aristolochene synthase (TEAS) from Nicotiana tabacum were incubated with 11 synthetic prenyl analogs with ether, thioether, alkyne, or phenyl groups, and six of them (60–65) were converted into several novel monoterpenoids 66–71 [46] (Figure 5). In addition to

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

• , thioether substituents were installed in the presence of K2CO3. For alkylthiols, DMF was used, but arylthiols required milder conditions with MeOH and cooling to acquire regioselectivity to the C4 position which resulted in yields up to 91%. Oxidation with purified mCPBA (commercial mCPBA with 68% purity

Switchable molecular tweezers: design and applications

• Pablo Msellem,
• Maksym Dekthiarenko,
• Nihal Hadj Seyd and
• Guillaume Vives

Beilstein J. Org. Chem. 2024, 20, 504–539, doi:10.3762/bjoc.20.45

• allosteric catalytic regulation (Figure 21). Mirkin and co-workers reported the symmetric tweezers 40 based on a Rh(I) complex with a phosphine and a labile thioether site and Cr(III)–salen arms as catalytic sites for the asymmetric ring opening of cyclohexene oxide by TMSN3 [80]. The closed tweezers showed

• higher activity and enantioselectivity due to the preorganization of the Cr(III) catalytic centers enabling bimetallic catalysis compared to the more flexible arrangement of the salen in the open form. The tweezers could be opened by breaking the thioether–rhodium bond with a combination of Cl− and CO

• metalloporphyrin arms [83] or larger assemblies [78]. In particular, remarkable double tweezers (or triple-decker catalysts) 41 have been developed (Figure 22). These tweezers consist of two Rh(I) complexes, wherein a catalytically active metal Al(III)–salen arm is shared on the phosphine thioether ligand side

Pseudallenes A and B, new sulfur-containing ovalicin sesquiterpenoid derivatives with antimicrobial activity from the deep-sea cold seep sediment-derived fungus Pseudallescheria boydii CS-793

• Zhen Ying,
• Xiao-Ming Li,
• Sui-Qun Yang,
• Hong-Lei Li,
• Xin Li,
• Bin-Gui Wang and
• Ling-Hong Meng

Beilstein J. Org. Chem. 2024, 20, 470–478, doi:10.3762/bjoc.20.42

• alkaloids containing an unprecedented spiro[bicyclo[2.2.2]octane-diketopiperazine] skeleton, chevalinulins A and B, and the first cytochalasin homodimer containing a thioether bridge, verruculoid A, were identified from deep-sea cold seeps-derived fungi and were described to have potent proangiogenic and

• . proliferatum with MIC values of 2, 4, and 4 μg/mL, respectively. Conclusion In conclusion, two new ovalicin sesquiterpenoid derivatives with a thioether bond, namely, pseudallenes A (1) and B (2), together with three known analogues 3–5, were isolated and identified from the cold seep-derived fungus P. boydii

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

• corresponding bis(thiophenyl) thioether, which then underwent successive bromination and iodination to give intermediate 18. Next, a two-fold Suzuki–Miyaura cross-coupling occurring chemoselectively on the iodinated positions allowed the symmetric extension of the hydrocarbon scaffold, with the insertion of two

Nucleophilic functionalization of thianthrenium salts under basic conditions

• Xinting Fan,
• Duo Zhang,
• Xiangchuan Xiu,
• Bin Xu,
• Yu Yuan,
• Feng Chen and
• Pan Gao

Beilstein J. Org. Chem. 2024, 20, 257–263, doi:10.3762/bjoc.20.26

• investigate simple alkylamines (2s and 2t) as the substrates. In doing so, we could not isolate the corresponding amination products 3as and 3at. To showcase the practical utility of our metal-free thioether formation process, we conducted a 5.0 mmol scale reaction and obtained the target product 3aa in 69

Copper-promoted C5-selective bromination of 8-aminoquinoline amides with alkyl bromides

• Changdong Shao,
• Chen Ma,
• Li Li,
• Jingyi Liu,
• Yanan Shen,
• Chen Chen,
• Qionglin Yang,
• Tianyi Xu,
• Zhengsong Hu,
• Yuhe Kan and
• Tingting Zhang

Beilstein J. Org. Chem. 2024, 20, 155–161, doi:10.3762/bjoc.20.14

• probable mechanism is proposed. As shown in Scheme 5, ethyl bromoacetate (2a) undergoes attack by the dipolar aprotic solvent DMSO to afford the intermediate A. This intermediate then reacts with the bromine anion to give intermediate B. Dimethylsulfonium bromide or dimethyl thioether/molecular bromine

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

• ) produced successively the lyso derivative 10.8 and the acetylated compound 10.9. The suppression of the ether function in position sn-1 of PAF or its replacement by a thioether function were also reported in 1984 with the aim to identify new compounds that could modulate platelet aggregation or featuring

• ) where the molecular structure is altered. However, the incorporation of a saccharide unit or an inositol moiety is included in subsequent sections. Modulation sn-1: In 1986, Morris-Natschke et al. [129][130] reported a racemic synthesis of thioether analogues of edelfosine using thioglycerol as

• iodomethane to give 26.2. 26.3 was isolated after the deprotection of the primary alcohol with BF3. Then, the installation of the phosphocholine polar head used POCl3 and choline tosylate to produce in low yield the phosphocholine thioether lipid 26.4. In this study, the authors reported that compound 26.4

Dipeptide analogues of fluorinated aminophosphonic acid sodium salts as moderate competitive inhibitors of cathepsin C

• Karolina Wątroba,
• Małgorzata Pawełczak and
• Marcin Kaźmierczak

Beilstein J. Org. Chem. 2023, 19, 434–439, doi:10.3762/bjoc.19.33

• ]. Based on its structure, many other inhibitors have been developed, such as vinyl sulfones, fluoromethyl ketones, and semicarbazides [8][9]. These inhibitors covalently bind to the nucleophilic thiol group of Cys234 in the active site of cathepsin C via a thioether bond. Phosphonates have been identified

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

• -unsaturated ester 42. Conversion of the installed alkene to the corresponding thioether followed by the reduction of the ester moiety using DIBAL gave the compound 43, which was subjected to a Stille coupling reaction [38] to yield compound 45. Hydrogenation reaction in the presence of metallic Mg [39

• ions. Further demethylation [40] and oxidation of the thioether followed by thermal elimination of the intermediate sulfoxide gave 2 in 98% yield after two steps (Scheme 7). The authors also achieved the synthesis of (±)-1 from combretastatin D-2 (2). Protection of the hydroxy group in compound 2 using

• (129) followed by the reduction [61] of the aldehyde gave the corresponding benzyl alcohol 131 in 76% yield. Deacetylation in the presence of hydrazine [62] followed by intramolecular thioetherification led to the macrocycle 133. Finally, the oxidation of the obtained thioether to the corresponding

1,4-Dithianes: attractive C2-building blocks for the synthesis of complex molecular architectures

• Bram Ryckaert,
• Ellen Demeyere,
• Frederick Degroote,
• Hilde Janssens and
• Johan M. Winne

Beilstein J. Org. Chem. 2023, 19, 115–132, doi:10.3762/bjoc.19.12

• co-workers could offer more opportunities here (Scheme 7) [43][44]. Furthermore, some recently reported photoredox-catalyzed thioether (C–H) alkylation and heteroarylation reactions developed by Alfonzo and Hande have demonstrated the use of 1,4-dithianes as viable substrates in such attractive bond

Practical synthesis of isocoumarins via Rh(III)-catalyzed C–H activation/annulation cascade

• Qian-Ci Gao,
• Yi-Fei Li,
• Jun Xuan and
• Xiao-Qiang Hu

Beilstein J. Org. Chem. 2023, 19, 100–106, doi:10.3762/bjoc.19.10

• , trifluoromethyl and nitro substituents, were retained unchanged in the final products (3ja, 3ka, 3ma, and 3na). Also the strongly coordinating thioether substituent proved to be suitable for this protocol, providing the desired product 3ea in 76% yield. Moreover, under the standard conditions, 3-thienyl and 2

Peptide stapling by late-stage Suzuki–Miyaura cross-coupling

• Hendrik Gruß,
• Rebecca C. Feiner,
• Ridhiwan Mseya,
• David C. Schröder,
• Michał Jewgiński,
• Kristian M. Müller,
• Rafał Latajka,
• Antoine Marion and
• Norbert Sewald

Beilstein J. Org. Chem. 2022, 18, 1–12, doi:10.3762/bjoc.18.1

• ], disulfide- [13], thioether- [14][15][16][17][18][19][20], triazole- [21][22], oxime- [23] and hydrazone formation [24] as well as multicomponent reactions such as the Ugi- or Petasis reaction [25][26][27][28][29][30][31][32]. The content of helicity can moreover be changed by the introduction of a photo

• Supporting Information File 1, Figure S4). As a conclusion from those experiments, it was hypothesised that the linker might be too rigid resulting in a distorted structure, which has also been previously reported for thioether cross-linked cysteines bearing a biphenyl template within the staple [20]. Hence

Copper-catalyzed monoselective C–H amination of ferrocenes with alkylamines

• Zhen-Sheng Jia,
• Qiang Yue,
• Ya Li,
• Xue-Tao Xu,
• Kun Zhang and
• Bing-Feng Shi

Beilstein J. Org. Chem. 2021, 17, 2488–2495, doi:10.3762/bjoc.17.165

• %), largely due to the poison of copper catalyst by thioether. Acyclic amines were also tested and the amination products were obtained in low yields (4n, 18%; 4o, 15%). Unfortunately, primary amines and anilines were completely inert. Encouraged by the above results, we further tried to synthesize ferrocene

Enantioenriched α-substituted glutamates/pyroglutamates via enantioselective cyclopropenimine-catalyzed Michael addition of amino ester imines

• Zara M. Seibel,
• Jeffrey S. Bandar and
• Tristan H. Lambert

Beilstein J. Org. Chem. 2021, 17, 2077–2084, doi:10.3762/bjoc.17.134

• handles for derivatization and so represent important achievements for this method. In terms of additional functionality, we found that a thioether substrate could be engaged with reasonably good efficiency and enantioselectivity (Table 2, entry 11). On the other hand, while a nitrile was compatible with

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

Chemical approaches to discover the full potential of peptide nucleic acids in biomedical applications

• Nikita Brodyagin,
• Martins Katkevics,
• Venubabu Kotikam,
• Christopher A. Ryan and
• Eriks Rozners

Beilstein J. Org. Chem. 2021, 17, 1641–1688, doi:10.3762/bjoc.17.116