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

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

• ]. 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

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 and reactivity of azole-based iodazinium salts

• Thomas J. Kuczmera,
• Annalena Dietz,
• Andreas Boelke and
• Boris J. Nachtsheim

Beilstein J. Org. Chem. 2023, 19, 317–324, doi:10.3762/bjoc.19.27

• both C–I bonds giving the iodinated N-arylbenzimidazoles 6a and 6b as a mixture with 54% and 25% yield [37]. A ring opening/closing cascade reaction with elemental sulfur resulted in the formation of the imidazo[4,5,1-kl]phenothiazine (7a) in 47% yield. The corresponding phenoselenazine 7b and the

An efficient metal-free and catalyst-free C–S/C–O bond-formation strategy: synthesis of pyrazole-conjugated thioamides and amides

• Shubham Sharma,
• Dharmender Singh,
• Sunit Kumar,
• Vaishali,
• Rahul Jamra,
• Naveen Banyal,
• Deepika,
• Chandi C. Malakar and
• Virender Singh

Beilstein J. Org. Chem. 2023, 19, 231–244, doi:10.3762/bjoc.19.22

• -tethered thioamide and amide conjugates. The thioamides were generated by employing a three-component reaction of diverse pyrazole C-3/4/5 carbaldehydes, secondary amines, and elemental sulfur in a single synthetic operation. The advantages of this developed protocol refer to the broad substrate scope

• product isolation procedures [58][59][60][61][62]. In the recent past, our group also reported two methods towards the exploration of elemental sulfur for the formation of a sulfur-containing framework; however, these methods suffer from some drawbacks such as lack of diversity in starting substrate, need

• pyrazole C-3/C-5 amide conjugates. Fascinated by the immense pharmacological profiles of pyrazole, thioamide and amide derivatives, it was envisaged to develop a practical approach towards the synthesis of pyrazole-thioamide and pyrazole-amide conjugates. Elemental sulfur was explored as a sulfurating

Functionalization of imidazole N-oxide: a recent discovery in organic transformations

• Koustav Singha,
• Imran Habib and
• Mossaraf Hossain

Beilstein J. Org. Chem. 2022, 18, 1575–1588, doi:10.3762/bjoc.18.168

• reactions with elemental sulfur [23][24][25], resulting in the generation of non-enolizable imidazole-2-thiones. At first, the alkylation of 2-unsubstituted imidazole N-oxides 40 took place in the presence of an equimolar quantity of benzyl bromide in CH2Cl2 at rt providing the (N-benzyloxy)imidazolium

• salts 41. The latter underwent deprotonation in the presence of triethylamine in pyridine to generate the carbene intermediates 42 (Scheme 9). After that, the optically active imidazole-2-thiones 43 were obtained through the reaction with elemental sulfur. In CHCl3 solutions, the study of the optical

• followed by the treatment of elemental sulfur, through the formation of the optically active intermediate N-butoxyimidazol-2-ylidenes 46 (Scheme 10). Conclusion Although there is a limited number of reports for synthetic approaches using imidazole N-oxides as substrates, the procedures are highly diverse

First example of organocatalysis by cathodic N-heterocyclic carbene generation and accumulation using a divided electrochemical flow cell

• Daniele Rocco,
• Ana A. Folgueiras-Amador,
• Richard C. D. Brown and
• Marta Feroci

Beilstein J. Org. Chem. 2022, 18, 979–990, doi:10.3762/bjoc.18.98

• from the anodic electroactivity of the electrogenerated carbene. In order to have NHC accumulation in the catholyte, the Nafion membrane (cell separator) was pretreated with an alkaline solution. The formation of NHC was quantified as its reaction product with elemental sulfur. The NHC was successfully

• NHCs are generated in situ, where they may be used as basic or nucleophilic species. Due to the difficulty isolating highly reactive NHCs, the concentration of the obtained NHC solution can be determined indirectly by addition of elemental sulfur after the electrolysis, which realizes quantitative

• . Firstly, the conditions for electrogeneration of the carbene in flow were optimized, quantifying the amount of NHC by means of its reaction with elemental sulfur. All the experiments were carried out using a 0.1 M solution of BMImBF4 in acetonitrile as catholyte in a divided cell using Nafion® 438

Catalyzed and uncatalyzed procedures for the syntheses of isomeric covalent multi-indolyl hetero non-metallides: an account

• Ranadeep Talukdar

Beilstein J. Org. Chem. 2021, 17, 2102–2122, doi:10.3762/bjoc.17.137

• only, thus stating the requirement of acid for this Fischer indole synthesis. Elemental sulfur has also been utilized in preparing bis(indol-3-yl)sulfides under transition-metal compound catalyzed spontaneous oxidation of the central chalcogen atom. Such reactions were carried out by Shibahara (2014

• ) and Yang (2016) [82][83]. Both reactions used aerial oxygen as the oxidizing agent for sulfur (Scheme 15). Shibahara utilized 20 mol % copper(I) thiophene-2-carboxylate (CuTC) as the catalyst, where heating N-methylindole (1) with elemental sulfur in DMSO as solvent at 90 °C under aerial oxygen led to

• the desired product 101 in 49% yield [82]. Other copper catalysts such as CuCl or CuBr gave low yields, even when used with 2,2’-bipyridyl as the ligand. First, oxidation of copper(I) takes place, which interacts with elemental sulfur to “activate” it. A nucleophilic attack from N-methylindole (1) to

Beyond ribose and phosphate: Selected nucleic acid modifications for structure–function investigations and therapeutic applications

• Christopher Liczner,
• Kieran Duke,
• Gabrielle Juneau,
• Martin Egli and
• Christopher J. Wilds

Beilstein J. Org. Chem. 2021, 17, 908–931, doi:10.3762/bjoc.17.76

• monobenzoylethanedithiol. The 3'-phosphorothioamidites are incorporated into an oligonucleotide by standard solid-phase synthesis conditions, however, the oxidation step is replaced with sulfurization by elemental sulfur (Scheme 2) [85]. It should be noted that more efficient sulfurization agents exist with faster

Synthesis, structural characterization, and optical properties of benzo[f]naphtho[2,3-b]phosphoindoles

• Mio Matsumura,
• Takahiro Teramoto,
• Masato Kawakubo,
• Masatoshi Kawahata,
• Yuki Murata,
• Kentaro Yamaguchi,
• Masanobu Uchiyama and
• Shuji Yasuike

Beilstein J. Org. Chem. 2021, 17, 671–677, doi:10.3762/bjoc.17.56

• phosphorus atom of 2 was carried out; the results are shown in Scheme 1. The reaction of 2 with hydrogen peroxide or elemental sulfur afforded the corresponding phosphine oxide 3 and sulfide 4 in 92% and 88% yield, respectively. Treatment of 2 with methyl triflate afforded phospholium triflate 5 in 81% yield

Synthesis of purines and adenines containing the hexafluoroisopropyl group

• Viacheslav Petrov,
• Rebecca J. Dooley,
• Alexander A. Marchione,
• Elizabeth L. Diaz,
• Brittany S. Clem and
• William Marshall

Beilstein J. Org. Chem. 2020, 16, 2739–2748, doi:10.3762/bjoc.16.224

• equivalent of elemental sulfur (Scheme 1). A crude mixture of 2a and 2b (ratio 70:30) was isolated in 78% yield. Since the minor isomer 2b had a significantly higher solubility in hexane, washing of the crude mixture with hexane resulted in an enrichment of the major isomer 2a (ratio 2a/2b 95:5 after washing

• into the final product, with extrusion of elemental sulfur) is not well understood and may be more complex, involving additional steps. The mechanism clarification of the reaction of tetrakis(trifluoromethyl)-1,3-dithietane (1) with azoles (and anilines) does require further investigation. As was

Synthetic approaches to bowl-shaped π-conjugated sumanene and its congeners

• Shakeel Alvi and
• Rashid Ali

Beilstein J. Org. Chem. 2020, 16, 2212–2259, doi:10.3762/bjoc.16.186

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

Et₃N/DMSO-supported one-pot synthesis of highly fluorescent β-carboline-linked benzothiophenones via sulfur insertion and estimation of the photophysical properties

• Dharmender Singh,
• Vipin Kumar and
• Virender Singh

Beilstein J. Org. Chem. 2020, 16, 1740–1753, doi:10.3762/bjoc.16.146

• -metal-free strategy is presented to access novel β-carboline-tethered benzothiophenone derivatives from 1(3)-formyl-β-carbolines using elemental sulfur activated by Et3N/DMSO. This expeditious catalyst-free reaction proceeds through the formation of β-carboline-based 2-nitrochalcones followed by an

• multistep syntheses. To overcome these drawbacks, elemental sulfur has emerged as a surrogate approach, where it can be inserted in situ. In this context, several research groups are actively involved in the development of novel and efficient approaches for the synthesis of sulfur-containing heterocycles

• -nitrochalcone 1bA and elemental sulfur by testing different activators (Table 1). Recent findings revealed that a combination of an aliphatic amine with DMSO activated elemental sulfur for an electrophilic addition to generate thioaurones and benzothiophenes [59]. At 70 °C, the use of DIPEA in combination with

Recent advances in transition-metal-catalyzed incorporation of fluorine-containing groups

• Xiaowei Li,
• Xiaolin Shi,
• Xiangqian Li and
• Dayong Shi

Beilstein J. Org. Chem. 2019, 15, 2213–2270, doi:10.3762/bjoc.15.218

A novel three-component reaction between isocyanides, alcohols or thiols and elemental sulfur: a mild, catalyst-free approach towards O-thiocarbamates and dithiocarbamates

• András György Németh,
• György Miklós Keserű and
• Péter Ábrányi-Balogh

Beilstein J. Org. Chem. 2019, 15, 1523–1533, doi:10.3762/bjoc.15.155

• isothiocyanates, as valuable building blocks from isocyanides and sulfur is proposed, as well. The synthetic procedure suits the demand of a modern organic chemist, as it tolerates a wide range of functional groups, it is atom economic and easily scalable. Keywords: ditihiocarbamate; elemental sulfur

• -stable, environmentally benign, cheap and nontoxic elemental sulfur offers an alternative starting material to integrate sulfur into the product [69]. For a single molecule, Tan and co-workers showed isothiocyanate might be formed from an isocyanide by elemental sulfur in the presence of a base in low

• ][87] and reactions involving sulfur [88], herein, we describe a novel synthesis of O-thiocarbamates and dithiocarbamates via a three-component reaction of elemental sulfur, isocyanides and alcohols or thiols (Scheme 1). Moreover, during the investigation of the reaction mechanism, we have identified

Synthesis and selected transformations of 2-unsubstituted 1-(adamantyloxy)imidazole 3-oxides: straightforward access to non-symmetric 1,3-dialkoxyimidazolium salts

• Grzegorz Mlostoń,
• Małgorzata Celeda,
• Katarzyna Urbaniak,
• Marcin Jasiński,
• Vladyslav Bakhonsky,
• Peter R. Schreiner and
• Heinz Heimgartner

Beilstein J. Org. Chem. 2019, 15, 497–505, doi:10.3762/bjoc.15.43

• . Deprotonation of the latter with triethylamine in the presence of elemental sulfur allows the in situ generation of the corresponding imidazol-2-ylidene, which traps elemental sulfur yielding a 1,3-dihydro-2H-imidazole-2-thione as the final product. Keywords: alkoxyamines; imidazole N-oxides; imidazolium salts

• -thiones by trapping of elemental sulfur [26][32]. Treatment of the symmetric imidazolium salt 15 with triethylamine in pyridine solution in the presence of elemental sulfur led to the 1,3-dihydro-2H-imidazole-2-thione 17 isolated in 83% yield (Scheme 8). In the 1H NMR spectrum, two equivalent HC(4) and HC

• (5) atoms appeared at 6.69 ppm, and in the 13C NMR spectrum, the C(4) and C(5) atoms gave only one signal localized at 114.6 ppm. Apparently, deprotonation of the imidazolium cation results in the formation of the nucleophilic imidazol-2-ylidene 16, which in situ reacts with elemental sulfur

Hypervalent organoiodine compounds: from reagents to valuable building blocks in synthesis

• Gwendal Grelier,
• Benjamin Darses and
• Philippe Dauban

Beilstein J. Org. Chem. 2018, 14, 1508–1528, doi:10.3762/bjoc.14.128

• metal-free alternative to the previous methods of formation of sulfur heterocycles 70 has been reported by using elemental sulfur in the presence of cesium carbonate (Scheme 32) [72]. The strategy can be extended to the synthesis of the cyclic selenium analogs 71 by utilizing elemental selenium and

One hundred years of benzotropone chemistry

• Arif Dastan,
• Haydar Kilic and
• Nurullah Saracoglu

Beilstein J. Org. Chem. 2018, 14, 1120–1180, doi:10.3762/bjoc.14.98

Synthesis and photophysical properties of novel benzophospholo[3,2-b]indole derivatives

• Mio Matsumura,
• Mizuki Yamada,
• Atsuya Muranaka,
• Misae Kanai,
• Naoki Kakusawa,
• Daisuke Hashizume,
• Masanobu Uchiyama and
• Shuji Yasuike

Beilstein J. Org. Chem. 2017, 13, 2304–2309, doi:10.3762/bjoc.13.226

• ]indole 3 in 66% yield. Then, the chemical modification of the phosphorus atom of 3 was carried out and the results are shown in Scheme 2. The treatment of 3 with hydrogen peroxide, elemental sulfur, and elemental selenium afforded the corresponding phosphine oxide 4, sulfide 5, and selenide 6

Nucleic acids through condensation of nucleosides and phosphorous acid in the presence of sulfur

• Tuomas Lönnberg

Beilstein J. Org. Chem. 2016, 12, 670–673, doi:10.3762/bjoc.12.67

• elemental sulfur. Desulfurization and subsequent digestion of the products by P1 nuclease revealed that nearly 80% of the internucleosidic linkages thus formed were of the canonical 3´,5´-type. Keywords: H-phosphonate; nucleic acid; polymerization; phosphite; sulfurization; Introduction Arguably the most

• polymerization. Proposed oxidants for prebiotic phosphite chemistry include H2O2 and Fe(III). The present paper describes the polymerization of thymidine and triethylammonium phosphite, with elemental sulfur acting as the oxidant. Up to pentameric oligonucleotides with internucleosidic phosphorothioate linkages

• of predominantly 3´,5´-regiochemistry were formed by this method. Elemental sulfur may have been abundant on primitive Earth but its availability is limited by its poor solubility. In the present study this problem was addressed by carrying out the model reaction in toluene. On primitive Earth

Aluminacyclopentanes in the synthesis of 3-substituted phospholanes and α,ω-bisphospholanes

• Vladimir A. D’yakonov,
• Alevtina L. Makhamatkhanova,
• Rina A. Agliullina,
• Leisan K. Dilmukhametova,
• Tat’yana V. Tyumkina and
• Usein M. Dzhemilev

Beilstein J. Org. Chem. 2016, 12, 406–412, doi:10.3762/bjoc.12.43

• (10d), 1,4-bis(1-methylphospholan-3-yl)butane (10e), and 1,6-bis(1-phenylphospholan-3-yl)hexane (10с) in 85 % yields. Similarly to phospholanes 2a–h, the resulting bisphospholanes 10a–c readily react with H2O2 in chloroform or with elemental sulfur to furnish the corresponding bisphospholane 1,1

Dimethylamine as the key intermediate generated in situ from dimethylformamide (DMF) for the synthesis of thioamides

• Weibing Liu,
• Cui Chen and
• Hailing Liu

Beilstein J. Org. Chem. 2015, 11, 1721–1726, doi:10.3762/bjoc.11.187

• substrates produced the desired products with excellent isolated yields. Keywords: aldehydes; dimethylformamide (DMF); elemental sulfur; ketones; thioamides; Introduction Thioamides, a well-known structural element of many sulfur-containing molecules, synthetic agents [1][2], heterocycles, natural products

• , our group has developed an improved synthetic procedure to construct thioamides (Scheme 1). Results and Discussion Our initial efforts focused on the optimization of the reaction conditions by employing 4-methoxybenzaldehyde (1a) as a model reactant to interact with elemental sulfur and DMF (Table 1

Bis(vinylenedithio)tetrathiafulvalene analogues of BEDT-TTF

• Erdal Ertas,
• İlknur Demirtas and
• Turan Ozturk

Beilstein J. Org. Chem. 2015, 11, 403–415, doi:10.3762/bjoc.11.46

• produce 13 as a minor product through the intermediate 12 by the loss of elemental sulfur. The reaction of a series of 1,8-diketones with LR 15 or P4S10 was further explored in 2003 [53]. With both reactants, 1,4-dithiin 11 was obtained as a major and thiophene 13 as a minor product along with the side

• removal of elemental sulfur (Scheme 3). The other side products 18 and 19 were possibly formed from the reaction of 10 with 20, leading to formation of 23 and 24, rearrangement of which would then produce 18 and 19. Moreover, rearrangement of 10 via 25 would result in the formation of 16. The structures

Synthesis of dinucleoside acylphosphonites by phosphonodiamidite chemistry and investigation of phosphorus epimerization

• William H. Hersh

Beilstein J. Org. Chem. 2015, 11, 184–191, doi:10.3762/bjoc.11.19

• by elemental sulfur [43]. As shown in Scheme 3, oxidation of 12 and 13 with anhydrous tert-butyl hydroperoxide gave the acylphosphonates 14 and 15. These products were immediately hydrolyzed by addition of approximately 2 equiv of aqueous triethylammonium bicarbonate (TEAB) to give the H-phosphonate