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

• carbonyl compounds 168 can be achieved with N-thiophthalimides 14 and diaryl disulfides 47, respectively (Scheme 73) [104]. They remarked that the presence of B2pin2 was essential in the coupling reaction of disulfides with α,β-unsaturated carbonyl compounds 168. The sulfenylation involved a 1,4-addition

Derivatives of benzo-1,4-thiazine-3-carboxylic acid and the corresponding amino acid conjugates

• Péter Kisszékelyi,
• Tibor Peňaška,
• Klára Stankovianska,
• Mária Mečiarová and
• Radovan Šebesta

Beilstein J. Org. Chem. 2022, 18, 1195–1202, doi:10.3762/bjoc.18.124

• significantly accelerated by ultrasonic irradiation [16]. Cyclocondensation of 1,3-dicarbonyl compounds with substituted diaryl disulfides in water in the presence of β-cyclodextrin gave 2,3-disubstituted benzo-1,4-thiazines in 70–91% yield in 50 min [17]. A highly efficient visible-light-mediated one-pot

Selective synthesis of α-organylthio esters and α-organylthio ketones from β-keto esters and sodium S-organyl sulfurothioates under basic conditions

• Jean C. Kazmierczak,
• Roberta Cargnelutti,
• Thiago Barcellos,
• Claudio C. Silveira and
• Ricardo F. Schumacher

Beilstein J. Org. Chem. 2021, 17, 234–244, doi:10.3762/bjoc.17.24

• to prepare α-thiocarbonyl compounds. In this way, Bolm and collaborators elaborated a copper(II) acetate-catalyzed reaction of β-dicarbonyl compounds with diaryl disulfides (Scheme 1A) [50]. In 2017, Zou and co-workers described the preparation of α-thiocarbonyl compounds through a reaction of 1,3

• -dicarbonyl substrates with diaryl disulfides promoted by Cs2CO3 at 130 °C (Scheme 1B) [51]. A year later, Wang and co-workers demonstrated that β-dicarbonyl compounds could react with thiols at room temperature under an oxygen atmosphere in the presence of a base. This work also demonstrated an easy access

Synthesis of benzo[d]imidazo[2,1-b]benzoselenoazoles: Cs₂CO₃-mediated cyclization of 1-(2-bromoaryl)benzimidazoles with selenium

• Mio Matsumura,
• Yuki Kitamura,
• Arisa Yamauchi,
• Yoshitaka Kanazawa,
• Yuki Murata,
• Tadashi Hyodo,
• Kentaro Yamaguchi and
• Shuji Yasuike

Beilstein J. Org. Chem. 2019, 15, 2029–2035, doi:10.3762/bjoc.15.199

• Figure S2 in Supporting Information File 1). Cs2CO3-mediated C(Het)–S bond formations of a heteroazole such as imidazo[1,2-a]pyridine, oxadiazole, and benzimidazole with diaryl disulfides without a transition metal catalyst have previously been developed [18][19]. The key step in these reactions is

Insertion of [1.1.1]propellane into aromatic disulfides

• Robin M. Bär,
• Gregor Heinrich,
• Martin Nieger,
• Olaf Fuhr and
• Stefan Bräse

Beilstein J. Org. Chem. 2019, 15, 1172–1180, doi:10.3762/bjoc.15.114

• ]. Presumably, there are two factors contributing to the lowered yield. The bond dissociation energy (BDE) of dialkyldisulfides is higher than the BDE of diaryl disulfides [30]. Therefore lower concentrations of thiyl radicals are present to initiate the reaction. The second reason could be the absorption of

Synthesis of aryl cyclopropyl sulfides through copper-promoted S-cyclopropylation of thiophenols using cyclopropylboronic acid

• Emeline Benoit,
• Ahmed Fnaiche and
• Alexandre Gagnon

Beilstein J. Org. Chem. 2019, 15, 1162–1171, doi:10.3762/bjoc.15.113

• with the one obtained for the ortho-methyl product 1e. Compound 1o indicates some level of tolerance towards functional groups that can be used à posteriori to modify the product. Diaryl disulfides 26 were isolated in yields ranging from 2 to 36%, depending on the thiophenol. Attempts at S

β-Hydroxy sulfides and their syntheses

• Mokgethwa B. Marakalala,
• Edwin M. Mmutlane and
• Henok H. Kinfe

Beilstein J. Org. Chem. 2018, 14, 1668–1692, doi:10.3762/bjoc.14.143

• alkyl radicals than the corresponding diaryl disulfides and benzyl radicals, respectively, are presumed to be the reasons behind the failure of the reaction to work with aliphatic alkenes [67]. 3.3. Synthesis of masked β-hydroxy sulfides via difunctionalization of alkenes Alkenes are versatile

Photocatalytic formation of carbon–sulfur bonds

• Alexander Wimmer and
• Burkhard König

Beilstein J. Org. Chem. 2018, 14, 54–83, doi:10.3762/bjoc.14.4

• thiolated ether adduct. A new sulfenyl radical is generated in the last step and reacts with another alkoxyalkyl radical. A series of functionalized diaryl disulfides, containing electron-donating and withdrawing-groups and also sterically demanding substituents gave the respective products. Dialkyl

Chemoselective synthesis of diaryl disulfides via a visible light-mediated coupling of arenediazonium tetrafluoroborates and CS₂

• Jing Leng,
• Shi-Meng Wang and
• Hua-Li Qin

Beilstein J. Org. Chem. 2017, 13, 903–909, doi:10.3762/bjoc.13.91

• Jing Leng Shi-Meng Wang Hua-Li Qin School of Chemistry, Chemical Engineering and Life Science, Wuhan University of Technology, 205 Luoshi Road, Wuhan 430070, PR China 10.3762/bjoc.13.91 Abstract A highly efficient and chemoselective method for the synthesis of diaryl disulfides is developed via a

• tetrafluoroborates; carbon disulfide; chemoselectivity; diaryl disulfides; photocatalyst; Findings The development of methods for the functionalization of peptides and proteins under mild conditions is a current frontier in the fields of chemistry, biology and drug discovery [1][2][3][4]. Most of the

• , the development of methodologies for the synthesis of disulfides is rather desirable and many research groups have made great contributions to the synthesis of diaryl disulfides such as the Chandrasekaran group [9] and the Wacharasindhu group [10]. Indeed, the design of sustainable and useful

Synthesis and nucleophilic aromatic substitution of 3-fluoro-5-nitro-1-(pentafluorosulfanyl)benzene

• Javier Ajenjo,
• Martin Greenhall,
• Camillo Zarantonello and
• Petr Beier

Beilstein J. Org. Chem. 2016, 12, 192–197, doi:10.3762/bjoc.12.21

• fluorination of nitro-substituted diaryl disulfides leading to 3- or 4-nitro-1-(pentafluorosulfanyl)benzenes [7][8][9][10]. This reaction is conducted in tens of kilogram scale in industry. The second method is known as Umemoto’s synthesis and starts with aromatic thiols or diaryl disulfides which are

Pyridine-promoted dediazoniation of aryldiazonium tetrafluoroborates: Application to the synthesis of SF₅-substituted phenylboronic esters and iodobenzenes

• George Iakobson,
• Junyi Du,
• Alexandra M. Z. Slawin and
• Petr Beier

Beilstein J. Org. Chem. 2015, 11, 1494–1502, doi:10.3762/bjoc.11.162

• interest in this functional group. Synthetic methods towards aliphatic SF5-containing compounds are based on free radical addition of SF5Cl or SF5Br to unsaturated compounds [7][8][9], whereas aromatic derivatives are available either by the Umemoto’s two-step synthesis from diaryl disulfides or

Efficient Cu-catalyzed base-free C–S coupling under conventional and microwave heating. A simple access to S-heterocycles and sulfides

• Silvia M. Soria-Castro and
• Alicia B. Peñéñory

Beilstein J. Org. Chem. 2013, 9, 467–475, doi:10.3762/bjoc.9.50

• Method A. Representative procedure for the one-pot three-step synthesis of alkyl aryl sulfides, diaryl disulfides and asymmetric diaryl sulfides The reactions were carried out by using method A. After 24 h at 100 °C, KOt-Bu (1 mmol, 2 equiv) was added to the reaction mixture and stirred for 10 min. The

• microwave irradiation the time was drastically reduced to 2 h. Both procedures are simple and involve a low-cost catalytic system. This methodology was also applied to the “one-pot” synthesis of target heterocycles, such as 3H-benzo[c][1,2]dithiol-3-one and 2-methylbenzothiazole, alkyl aryl sulfides, diaryl

• disulfides and asymmetric diaryl sulfides in good yields. Keywords: catalysis; copper; cross-coupling; potassium thioacetate; sulfur heterocycles; Introduction Aromatic sulfur compounds including sulfides and heterocycles are relevant in chemical, pharmaceutical and materials industries [1][2][3]. As a

Highly selective synthesis of (E)-alkenyl-(pentafluorosulfanyl)benzenes through Horner–Wadsworth–Emmons reaction

• George Iakobson and
• Petr Beier

Beilstein J. Org. Chem. 2012, 8, 1185–1190, doi:10.3762/bjoc.8.131

• aromatic meta- and para-nitro-(pentafluorosufanyl)benzenes (1 and 2) are made by direct fluorination of the corresponding bis(nitrophenyl)disulfides [10][11][12]. A recent report also described a two step synthesis of SF5-benzenes from diaryl disulfides avoiding the use of elemental fluorine [13]. While

Discovery of practical production processes for arylsulfur pentafluorides and their higher homologues, bis- and tris(sulfur pentafluorides): Beginning of a new era of “super-trifluoromethyl” arene chemistry and its industry

• Teruo Umemoto,
• Lloyd M. Garrick and
• Norimichi Saito

Beilstein J. Org. Chem. 2012, 8, 461–471, doi:10.3762/bjoc.8.53

• the production of various arylsulfur pentafluorides and their higher homologues, bis- and tris(sulfur pentafluorides), from the corresponding diaryl disulfides or aryl thiols. The method consists of two steps: (Step 1) treatment of a diaryl disulfide or an aryl thiol with chlorine in the presence of

• industry. These new methods have been described in patents and patent applications [43][44][45][46][47][48]. Results and Discussion Recently we synthesized various arylsulfur trifluorides (ArSF3) by treatment of diaryl disulfides with chlorine in the presence of potassium [49][50] or cesium fluoride [50

• 13C NMR spectroscopy of the reaction solution. Arylsulfur chlorotetrafluorides were prepared in high yield by the reactions of diaryl disulfides with an excess amount of chlorine (ca. 7 mol or more per mole of the disulfide) in the presence of an excess amount of potassium or cesium fluoride (ca. 16

Aromatic and heterocyclic perfluoroalkyl sulfides. Methods of preparation

• Vladimir N. Boiko

Beilstein J. Org. Chem. 2010, 6, 880–921, doi:10.3762/bjoc.6.88

• -phenols, and diaryl disulfides with perfluoroalkyl iodides in liquid ammonia under UV irradiation Kornblum’s work on nucleophilic substitution in alkyl halides [134][135][136][137] and Bunnett’s reactions with non-activated aromatic substrates [138][139][140][141][142] (under UV irradiation) introduced

• chain results in lower yields of the corresponding sulfides (10–15%). In the case of tertiary perfluorobutyl iodide, thiophenols are quantitatively transformed into diaryl disulfides. Such behavior of branched perfluoroalkyl iodides can be explained by the facile generation of the I• radical both as a

• consequence of their homolytic decomposition [155] and the decomposition of in situ generated radical anions [156]: i-RFI−• → i-RF− + I•. The radical I• (or I2) oxidizes the ArS− anion to disulfide. Diaryl disulfides may also be used as substrates. Although they can be trifluoromethylated directly [157