Direct synthesis of acyl fluorides from carboxylic acids using benzothiazolium reagents

• Lilian M. Maas,
• Alex Haswell,
• Rory Hughes and
• Matthew N. Hopkinson

Beilstein J. Org. Chem. 2024, 20, 921–930, doi:10.3762/bjoc.20.82

• studied due to the easy accessibility of fluoride ions with many methods directly employing the parent carboxylic acid as substrate. These processes avoid an additional pre-functionalisation step and have been reported using a range of deoxyfluorinating reagents including (diethylamino)sulfur trifluoride

Synthesis and biological profile of 2,3-dihydro[1,3]thiazolo[4,5-b]pyridines, a novel class of acyl-ACP thioesterase inhibitors

• Jens Frackenpohl,
• David M. Barber,
• Guido Bojack,
• Birgit Bollenbach-Wahl,
• Ralf Braun,
• Rahel Getachew,
• Sabine Hohmann,
• Kwang-Yoon Ko,
• Karoline Kurowski,
• Bernd Laber,
• Rebecca L. Mattison,
• Thomas Müller,
• Anna M. Reingruber,
• Dirk Schmutzler and
• Andrea Svejda

Beilstein J. Org. Chem. 2024, 20, 540–551, doi:10.3762/bjoc.20.46

• quantities of the most active compounds for advanced biological testing. Pleasingly, our four-step approach using a potassium O-ethyl dithiocarbonate-mediated formation of thio intermediates 11a–c (thiol–thione tautomers) with subsequent sulfur removal using iron powder in acetic acid [19] proceeded smoothly

• : 10 plants per pot). Selected known inhibitors 1–3 of acyl-ACP thioesterases (belonging to the protein family of FATs) and new lead structures 4–7a. Preparation of 2,3-dihydro[1,3]thiazolo[4,5-b]pyridines 7a–c and 13a–c via iron-mediated sulfur removal and subsequent reduction. dppf = 1,1'-bis

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

• using metal complexes as switching units (Figure 20). This concept named “weak link approach” (WLA) [78] uses square planar d8-transition metal complexes with two hemilabile bidentate ligands composed of a strong binding site (phosphorus) and a weaker one (generally sulfur, oxygen, selenium, or nitrogen

A new analog of dihydroxybenzoic acid from Saccharopolyspora sp. KR21-0001

• Rattiya Janthanom,
• Yuta Kikuchi,
• Hiroki Kanto,
• Tomoyasu Hirose,
• Arisu Tahara,
• Takahiro Ishii,
• Arinthip Thamchaipenet and
• Yuki Inahashi

Beilstein J. Org. Chem. 2024, 20, 497–503, doi:10.3762/bjoc.20.44

• 129.4) and C-10 through a sulfur atom. Based on these results, the structure of 1 was elucidated as 4-((2-acetamido-2-carboxyethyl)thio)-2,3-dihydroxybenzoic acid. The absolute configuration of 1 was determined by advanced Marfey’s analysis. 1 was de-sulfurized with skeletal Ni and then hydrolyzed with

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

• sulfur-containing ovalicin derivatives, along with three known analogues 3–5, were isolated and identified from the culture extract of Pseudallescheria boydii CS-793, a fungus obtained from the deep-sea cold seep sediments. Their structures were established by detailed interpretation of NMR spectroscopic

• -rich fluid emissions and unique sulfur oxidation–reduction reactions [1]. Due to the unique habitat, microorganisms surviving in the deep-sea cold seeps may serve as promising sources of secondary metabolites with functional and structural diversity [2]. In particular, two indole diketopiperazine

• our attention. Several meroterpenoids, alkaloids, polyketides, and sesquiterpenoids from the species displayed various biological properties including anti-inflammatory, antimicrobial, and cytotoxic activities [7][8][9]. In the present work, two rare new examples of sulfur-containing ovalicin

(E,Z)-1,1,1,4,4,4-Hexafluorobut-2-enes: hydrofluoroolefins halogenation/dehydrohalogenation cascade to reach new fluorinated allene

• Nataliia V. Kirij,
• Andrey A. Filatov,
• Yurii L. Yagupolskii,
• Sheng Peng and
• Lee Sprague

Beilstein J. Org. Chem. 2024, 20, 452–459, doi:10.3762/bjoc.20.40

• demonstrated that 1,1,1,4,4,4-hexafluorobut-2-ene reacts with dithietane, sulfur and KF with the formation of the corresponding 1,3-dithiole [16]. Also, a recent patent presents a method for the preparation of 5,6-bis(trifluoromethyl)-1,2,4-triazine-3-carboxylic acid ethyl ester starting from 1,1,1,4,4,4

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

• sulfur extrusion [44]. It appeared that thiepines carrying sterically demanding substituents on the sulfur α-positions as well as annelated analogues show substantially increased lifetimes, owing to steric and electronic effects [45]. With these criteria in mind, a variety of thermally-stable annelated

• thiepines were progressively isolated as a result of very diverse synthetic strategies [46][47][48][49], which were further applied to the preparation of stable selenepines and tellurepines [50][51][52][53]. Extrusion reactions from sulfur-, selenium- and tellurium-containing compounds have long been

• , 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

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

• , the scope of sulfonium salts was examined, as summarized in Scheme 2a. Alkylsulfonium salts substituted with a halide (F, Cl, or Br) or isocyano group at the para-position of the aryl ring (1b–e) were successfully converted into the carbon–sulfur bond formation products (3ba–fa) in moderate to good

Synthesis of the 3’-O-sulfated TF antigen with a TEG-N₃ linker for glycodendrimersomes preparation to study lectin binding

• Mark Reihill,
• Hanyue Ma,
• Dennis Bengtsson and
• Stefan Oscarson

Beilstein J. Org. Chem. 2024, 20, 173–180, doi:10.3762/bjoc.20.17

• glycosylation reactions. The 3’-sulfate was finally introduced through tin activation in benzene/DMF followed by treatment with a sulfur trioxide–trimethylamine complex in a 66% yield. Keywords: regioselective sulfation; thioglycoside donors; Thomsen–Friedenreich antigen; Introduction In a collaboration

Aldiminium and 1,2,3-triazolium dithiocarboxylate zwitterions derived from cyclic (alkyl)(amino) and mesoionic carbenes

• Nedra Touj,
• François Mazars,
• Guillermo Zaragoza and
• Lionel Delaude

Beilstein J. Org. Chem. 2023, 19, 1947–1956, doi:10.3762/bjoc.19.145

• charge of the CS2− unit was uniformly delocalized between the two sulfur atoms (Table 3). Moreover, the average length of 1.67 Å recorded for all the C–S bonds matched the typical distance compiled for double rather than single CS bonds (1.67 vs 1.75 Å) [78]. At (130 ± 1)°, the S1–C1–S2 bite angle of the

• attractive coulombic interactions between the opposite charges were held responsible for this orientation [79]. In addition, the presence of bulky aryl substituents in the vicinity of the sulfur atoms should further restrict their conformational freedom. As a matter of fact, the largest deviation from

Thienothiophene-based organic light-emitting diode: synthesis, photophysical properties and application

• Recep Isci and
• Turan Ozturk

Beilstein J. Org. Chem. 2023, 19, 1849–1857, doi:10.3762/bjoc.19.137

• synthesis commenced with the treatment of 3-bromothiophene (1) with n-butyllithium at −78 °C, followed by the addition of elemental sulfur and subsequent reaction with 2-bromo-1-(4-methoxyphenyl)ethanone to produce compound 2 in 83% yield. The following ring-closure reaction was conducted in the presence of

Tying a knot between crown ethers and porphyrins

• Maksym Matviyishyn and
• Bartosz Szyszko

Beilstein J. Org. Chem. 2023, 19, 1630–1650, doi:10.3762/bjoc.19.120

• /electrostatic interactions [18][19][20]. Replacing oxygen atoms with other elements, such as nitrogen, sulfur, etc., alters the crown ethers' affinity toward cations, extending their role as macrocyclic ligands to transition metals [21]. One can say that in many aspects, porphyrins and crown ethers are

Sulfur-containing spiroketals from Breynia disticha and evaluations of their anti-inflammatory effect

• Ken-ichi Nakashima,
• Naohito Abe,
• Masayoshi Oyama,
• Hiroko Murata and
• Makoto Inoue

Beilstein J. Org. Chem. 2023, 19, 1604–1614, doi:10.3762/bjoc.19.117

• Pharmaceutical University, 1-25-4 Daigaku-nishi, Gifu 501-1196, Japan retired, formerly Faculty of Pharmaceutical Sciences, Setsunan University, 45-1 Nagaotoge-cho, Hirakata, Osaka, 573-0101, Japan 10.3762/bjoc.19.117 Abstract Breynia spp. are a key source of sulfur-containing spiroketal glycosides with

• potential anti-inflammatory activity. In this study, three new sulfur-containing spiroketals – breynin J (1), epibreynin J (2), and probreynogenin (3) – along with four known compounds – probreynin I (4), phyllaemblic acid (5), breynin B (6), and epibreynin B (7) – were isolated from the roots of Breynia

• potent compound 7 was found to significantly inhibit the production of IL-1β and IL-6 proteins, as revealed by the analysis of culture supernatants. Keywords: anti-inflammatory; Breynia disticha; RAW 264.7 cells; sesquiterpenoids; sulfur-containing compounds; Introduction Breynia disticha J.R.Forst

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

• high refractive-index polymers. A common approach is to incorporate atoms or groups with high polarizability and sulfur is a typical constituent with high molar refractivity and is widely used in optical polymers. For example, Bhagat et al. [84] produced polymers with high cross-linking density and

• 1830s, Charles Goodyear invented vulcanized rubber. By heating natural rubber with lead oxide and sulfur, the temperature-sensitive rubber became a more stable material, even at high and low temperatures, while keeping the elasticity, plasticity, insulation, and other excellent characteristics [124

• ]. During the vulcanization of natural rubber, elemental sulfur was heated to form sulfur radicals which then react with natural rubber crosslinking two independent polymer molecules [125]. This is a typical example of polymer crosslinking by a radical mechanism. As the traditional vulcanization process, an

N-Sulfenylsuccinimide/phthalimide: an alternative sulfenylating reagent in organic transformations

• Fatemeh Doraghi,
• Seyedeh Pegah Aledavoud,
• Mehdi Ghanbarlou,
• Bagher Larijani and
• Mohammad Mahdavi

Beilstein J. Org. Chem. 2023, 19, 1471–1502, doi:10.3762/bjoc.19.106

• article, we focus on the application of these alternative sulfenylating reagents in organic transformations. Keywords: electrophile; N-(sulfenyl)succinimides/phthalimides; organic transformations; organosulfur; sulfenylation; Introduction Sulfur-containing compounds are of high importance in organic

• synthesis, medicinal chemistry, and materials science [1][2][3][4][5]. For example, they are used in the treatment of cancer [6][7][8], inflammation [9][10][11], human immunodeficiency virus [12][13], Alzheimer’s and Parkinson’s diseases [14][15]. Scheme 1 shows selected examples of sulfur-containing

• pharmaceutical molecules. Considering the synthetic applications of sulfur-based compounds, a large number of researchers have noted that these scaffolds have promising potential for the research and development of new biomedicines. In the sulfenylation of organic compounds, the sulfenylating agents are

Application of N-heterocyclic carbene–Cu(I) complexes as catalysts in organic synthesis: a review

• Nosheen Beig,
• Varsha Goyal and
• Raj K. Bansal

Beilstein J. Org. Chem. 2023, 19, 1408–1442, doi:10.3762/bjoc.19.102

• reaction of the carbene 1,3-dimesitylimidazol-2-ylidene (7a) with carbon tetrachloride in THF (Scheme 4) [5]. Structure of N-heterocyclic carbenes N-Heterocyclic carbenes contain at least one nitrogen atom and there may be another nitrogen atom or a sulfur atom present in the heterocycle. A general

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

Non-noble metal-catalyzed cross-dehydrogenation coupling (CDC) involving ether α-C(sp³)–H to construct C–C bonds

• Hui Yu and
• Feng Xu

Beilstein J. Org. Chem. 2023, 19, 1259–1288, doi:10.3762/bjoc.19.94

• -catalyzed formation of 1,1-bis-indolylmethane derivatives. Alkylation of coumarins and flavonoids. Direct CDC α-arylation of azoles with ethers. CDC of terminal alkynes with C(sp3)–H bonds adjacent to oxygen, sulfur or nitrogen atoms. Alkylation of terminal alkynes. Co-catalyzed functionalization of glycine

New one-pot synthesis of 4-arylpyrazolo[3,4-b]pyridin-6-ones based on 5-aminopyrazoles and azlactones

• Vladislav Yu. Shuvalov,
• Ekaterina Yu. Vlasova,
• Tatyana Yu. Zheleznova and
• Alexander S. Fisyuk

Beilstein J. Org. Chem. 2023, 19, 1155–1160, doi:10.3762/bjoc.19.83

• aldehyde with thioglycolic acid and aminopyrazole, followed by the extrusion of sulfur from the resulting thiazepine [20] (method C). The three-stage synthesis of 4-arylpyrazolo[3,4-b]pyridin-6-ones, involving the preparation of 3-aryl-N-(1H-pyrazol-5-yl)propiolamides (method D), also leads to the

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

• ) significantly slowed down the reaction. Gratifyingly, we observed excellent selectivity for substrates that contained an additional sulfur atom in the structure. Thus, thianthrene selectively generated product 2c, which is an important precursor for the synthesis of thianthrene salts [37]. To our delight, the

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

• direct application of commercially available potassium (poly)sulfide (K2Sx) with H2O, the top-down generation from elemental sulfur (S8) with sodium tert-butoxide (NaOt-Bu), and the bottom-up generation from lithium sulfide (Li2S) or triisopropylsilanethiol (iPr3SiSH) were all suitable methods of

Synthesis of imidazo[4,5-e][1,3]thiazino[2,3-c][1,2,4]triazines via a base-induced rearrangement of functionalized imidazo[4,5-e]thiazolo[2,3-c][1,2,4]triazines

• Dmitry B. Vinogradov,
• Alexei N. Izmest’ev,
• Angelina N. Kravchenko,
• Yuri A. Strelenko and
• Galina A. Gazieva

Beilstein J. Org. Chem. 2023, 19, 1047–1054, doi:10.3762/bjoc.19.80

• rearrangement; 1,3-thiazines; thiazolidine-4-ones; Introduction Nitrogen- and sulfur-containing heterocyclic compounds are widely represented in nature and used for the synthesis of biologically active substances. Among the 1,3-thiazine derivatives, promising compounds as antimicrobial and antiviral drugs

The effect of dark states on the intersystem crossing and thermally activated delayed fluorescence of naphthalimide-phenothiazine dyads

• Liyuan Cao,
• Xi Liu,
• Xue Zhang,
• Jianzhang Zhao,
• Fabiao Yu and
• Yan Wan

Beilstein J. Org. Chem. 2023, 19, 1028–1046, doi:10.3762/bjoc.19.79

• the energy ordering of the transient species involved in the TADF photophysical process, the electron-donating strength of the PTZ moiety is lowered by oxidation of the sulfur atom to the corresponding sulfoxide. Conversely, the electron-accepting capability of the NI unit is varied by introducing

• substituents on the NI unit (NI-PTZ-F, NI-PTZ-Ph, NI-PTZ-CH3, NI-PTZ-OCH3), and the electron-donating ability of the PTZ unit was modified by oxidation of the sulfur atom to the sulfoxide (NI-PTZ-F-O, NI-PTZ-Ph-O, NI-PTZ-C5-O). The advantage of the oxidation approach is that almost only the energy of the 1CS

Clauson–Kaas pyrrole synthesis using diverse catalysts: a transition from conventional to greener approach

• Dileep Kumar Singh and
• Rajesh Kumar

Beilstein J. Org. Chem. 2023, 19, 928–955, doi:10.3762/bjoc.19.71

• -arylpyrroles were converted to the corresponding thiocyanated derivatives and then to sulfur-containing heterocycles. Moreover, this procedure provides N-substituted pyrroles from various aromatic amines in good to excellent yields under both reflux and MW conditions. In contrast, aliphatic amines such as

Synthesis of aliphatic nitriles from cyclobutanone oxime mediated by sulfuryl fluoride (SO₂F₂)

• Xian-Lin Chen and
• Hua-Li Qin

Beilstein J. Org. Chem. 2023, 19, 901–908, doi:10.3762/bjoc.19.68

• (SO2F2) [43], a kind of inexpensive (about 1 $/kg), abundant, and relatively inert electrophile and one of the major sulfur fluoride exchange (SuFEx) click chemistry reagents [44][45], has been successfully applied as an electrophile to react with hydroxy groups to generate fluorosulfonate esters, being