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

• studies indicate that thiosulfonates play an important role in the reaction process. Keywords: disulfides; sodium sulfinates; 3-sulfenylchromones; TBAI; thiosulfonates; Introduction Organosulfur compounds containing S–S bonds, often referred to as disulfides, are among the most valuable functional

• (sp2)–H radical sulfenylation of enaminones or chromones has emerged as a popular strategy using various sulfenyl precursors such as thiophenols [38][39][40], sulfonyl hydrazides [41][42], disulfides [43], KSCN [44], S8 [45], methylsulfinyl derivatives [46], sodium sulfinates [47], and thiosulfonates

• this study, we report the synthesis of corresponding disulfides under the catalysis of TBAI (tetrabutylammonium iodide) using sodium alkyl or aromatic sulfinates as sulfur sources. Sodium sulfinates are more stable than sulfonyl hydrazides, sulfonyl chlorides, and thiols, and there is no need to add

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

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

• group of the iodonium salt was also investigated. A potential radical-mediated mechanism was evaluated. Under mild conditions, a base-promoted arylation of general sulfinates 86 without the need for transition metals was introduced using diaryliodonium salts 16 as an aryl source (Scheme 35). Inspired by

C–H Trifluoromethylthiolation of aldehyde hydrazones

• Victor Levet,
• Balu Ramesh,
• Congyang Wang and
• Tatiana Besset

Beilstein J. Org. Chem. 2024, 20, 2883–2890, doi:10.3762/bjoc.20.242

• aldehyde hydrazones using sodium sulfinates. These seminal works brought interesting proofs of concept for the synthesis of SR-containing hydrazones. Inspired by these previous works and taking benefit from our in-home expertise to forge N–SCF3 bond (after chlorination/anion metathesis with AgSCF3 from the

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

• transformed into a series of useful molecules, enabling them an important backbone in organic synthesis. Lin et al. [66] used sodium sulfinates as the nucleophiles to realize the asymmetric sulfonylation of yne-allylic esters. The reaction can be carried out under mild conditions with good to excellent regio

Harnessing the versatility of hydrazones through electrosynthetic oxidative transformations

• Aurélie Claraz

Beilstein J. Org. Chem. 2024, 20, 1988–2004, doi:10.3762/bjoc.20.175

• aldehyde-derived N,N-dialkylhydrazones 123 under constant current with two carbon electrodes. Aromatic and aliphatic sodium sulfinates 124 were employed as sources of sulfinate radicals under electrolyte-free reaction conditions. The targeted product was obtained in high yield regardless of the electronic

Mechanistic investigations of polyaza[7]helicene in photoredox and energy transfer catalysis

• Johannes Rocker,
• Till J. B. Zähringer,
• Matthias Schmitz,
• Till Opatz and
• Christoph Kerzig

Beilstein J. Org. Chem. 2024, 20, 1236–1245, doi:10.3762/bjoc.20.106

• its photochemical reactivity. The main reaction class catalyzed by excited-state polyazahelicene Aza-H so far is the redox-neutral addition of sulfinates and cyanopyridines, under elimination of cyanide, to styrenes in a three-component reaction. The proposed mechanism was derived from the redox

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

• preparation of 2-chloro-4-sulfonylquinazolines 8 (Scheme 3). The starting material 7 underwent SNAr reactions with sodium sulfinates and the C4-substituted products 8a,b were isolated [24]. The complete conversion was achieved in DMF or DMSO. In the case of sodium dodecylsulfinate, the reaction stopped at 70

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

• -catalyzed sulfenylation by N-(sulfenyl)succinimides/phthalimides In 2012, Chen and co-workers found that in the reaction of N-(organothio)succinimides 1 and sodium sulfinates 2 using a Lewis acid in ionic liquids (ILs) and water as a green solvent system leads to the formation of thiosulfonates 3 (Scheme 2

Heterogeneous metallaphotoredox catalysis in a continuous-flow packed-bed reactor

• Wei-Hsin Hsu,
• Susanne Reischauer,
• Peter H. Seeberger,
• Bartholomäus Pieber and
• Dario Cambié

Beilstein J. Org. Chem. 2022, 18, 1123–1130, doi:10.3762/bjoc.18.115

• (catalyst) separation in one step. The use of a packed bed simplifies the translation of optimized batch reaction conditions to continuous flow, as the only components present in the reaction mixture are the substrate and a base. The metallaphotoredox cross-coupling of sulfinates with aryl halides was used

• as a model system. The catalyst was shown to be stable, with a very low decrease of the yield (≈1% per day) during a continuous experiment over seven days, and to be effective for C–O arylations when carboxylic acids are used as nucleophile instead of sulfinates. Keywords: flow chemistry

• light-mediated carbon–heteroatom cross-couplings of sodium sulfinates, carboxylic acids and sulphonamides with aryl halides (Figure 2) [28]. Although recyclable, batch reactions are characterized by long reaction times (24 h). Here, we present a detailed investigation of a continuous-flow strategy for

Synthesis of α-(perfluoroalkylsulfonyl)propiophenones: a new set of reagents for the light-mediated perfluoroalkylation of aromatics

• Durbis J. Castillo-Pazos,
• Juan D. Lasso and
• Chao-Jun Li

Beilstein J. Org. Chem. 2022, 18, 788–795, doi:10.3762/bjoc.18.79

• , perfluorohexylation, and perfluorobutylation. Keywords: α-(perfluoroalkylsulfonyl)propiophenones; innate functionalization; late-stage functionalization; light-mediated perfluoroalkylation; perfluoroalkyl sulfinates; Introduction Perfluorinated compounds are a family of molecules containing a backbone where all C–H

Mechanistic studies of the solvolysis of alkanesulfonyl and arenesulfonyl halides

• Malcolm J. D’Souza and
• Dennis N. Kevill

Beilstein J. Org. Chem. 2022, 18, 120–132, doi:10.3762/bjoc.18.13

• defining mechanisms of nucleophilic substitution at sulphur are known to the writer...”. Examination of this section of the text shows, however, that it is limited to a consideration of substitution at the sulfur of sulfinates and reactions of the general type illustrated in Equation 3 and reactions

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

• a mild and efficient protocol for the remote C4–H sulfonylation of 1-naphthylamine derivatives with sodium sulfinates in the presence of K2S2O8 as the oxidant (Figure 35) [99]. This strategy was based on the use of a bidentate picolinamide DG promoting the direct C–H functionalization of the

• procedure was general and both electron-withdrawing or -donating substituents were well tolerated at different positions of the 1-naphthylamine derivatives. Aromatic, aliphatic as well as heterocyclic sodium sulfinates were also suitable coupling partners for this C–H functionalization. In addition, the

Photocatalyzed syntheses of phenanthrenes and their aza-analogues. A review

• Alessandra Del Tito,
• Havall Othman Abdulla,
• Davide Ravelli,
• Stefano Protti and
• Maurizio Fagnoni

Beilstein J. Org. Chem. 2020, 16, 1476–1488, doi:10.3762/bjoc.16.123

• desired trifluoromethylated products 7.3a–d in satisfactory yields (Scheme 7, path a) [57]. Tri-, di-, and monofluoroalkylated derivatives were also obtained by using fluoroalkyl heteroaryl sulfones [58] or sodium sulfinates (in the presence of persulfate) [59] as the alkylating agents. In an alternative

Oxime radicals: generation, properties and application in organic synthesis

• Igor B. Krylov,
• Stanislav A. Paveliev,
• Alexander S. Budnikov and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2020, 16, 1234–1276, doi:10.3762/bjoc.16.107

• -position (R1, R2 = Me), as well as oximes having a disubstituted double bond, also give cyclization products with good yields (products 152b,c). The interaction of β,γ-unsaturated oximes 153 with sodium sulfinates in the presence of copper(II) acetate leads to substituted isoxazolines 154 with the sulfonyl

• compared to para- and meta-substituted substrates. In addition to sodium aryl sulfinates, sodium methane sulfinate was used for the synthesis of product 154h in good yield. The presence of an electron-withdrawing group in the aromatic ring of sulfinate decreases the yield (product 154f compared to product

Photocatalysis with organic dyes: facile access to reactive intermediates for synthesis

• Stephanie G. E. Amos,
• Marion Garreau,
• Luca Buzzetti and
• Jerome Waser

Beilstein J. Org. Chem. 2020, 16, 1163–1187, doi:10.3762/bjoc.16.103

Recent applications of porphyrins as photocatalysts in organic synthesis: batch and continuous flow approaches

• Rodrigo Costa e Silva,
• Luely Oliveira da Silva,
• Aloisio de Andrade Bartolomeu,
• Timothy John Brocksom and
• Kleber Thiago de Oliveira

Beilstein J. Org. Chem. 2020, 16, 917–955, doi:10.3762/bjoc.16.83

• -rich and electron-deficient groups in the arylsulfinic acid and alkyl sulfinates, such as sodium ethylsulfinate and sodium methylsulfinate (Scheme 19). The authors also showed that the methodology can be applied to the sulfonation of steroid drug arimistane in 45% yield (Scheme 20). The mechanistic

Syntheses and chemical properties of β-nicotinamide riboside and its analogues and derivatives

• Mikhail V. Makarov and
• Marie E. Migaud

Beilstein J. Org. Chem. 2019, 15, 401–430, doi:10.3762/bjoc.15.36

• ]. Mechanistic studies of Na2S2O4 reduction of pyridinium salts, including NR+ derivatives, suggest that this reaction proceeds through the formation of sulfinic acid adducts (1,4-dihydro-4-pyridine sulfinates) I. This adduct is generated from the completely regioselective attack of the dithionite ion on the 4

Oxidative radical ring-opening/cyclization of cyclopropane derivatives

• Yu Liu,
• Qiao-Lin Wang,
• Zan Chen,
• Cong-Shan Zhou,
• Bi-Quan Xiong,
• Pan-Liang Zhang,
• Chang-An Yang and
• Quan Zhou

Beilstein J. Org. Chem. 2019, 15, 256–278, doi:10.3762/bjoc.15.23

• sulfonylation of teriary cyclopropanols 91 with sodium sulfinates 129 for the synthesis of γ-keto sulfones 130 in excellent yields (Scheme 34) [114]. The reaction was compatible with a series of fluoroalkyl, aryl and alkyl sulfinate salts. Notably, oxygen instead of THBP as oxidation was viable in this

Rapid transformation of sulfinate salts into sulfonates promoted by a hypervalent iodine(III) reagent

• Elsa Deruer,
• Vincent Hamel,
• Samuel Blais and
• Sylvain Canesi

Beilstein J. Org. Chem. 2018, 14, 1203–1207, doi:10.3762/bjoc.14.101

• hypervalent iodine(III) reagent-mediated oxidation of sodium sulfinates has been developed. This transformation involves trapping reactive sulfonium species using alcohols. With additional optimization of the reaction conditions, the method appears extendable to other nucleophiles such as electron-rich

• aromatic systems or cyclic ethers through a ring opening pathway. Keywords: hypervalent iodine; oxidation; sulfinates; sulfonation; sulfonium; Introduction Over the past few decades, hypervalent iodine reagents [1][2][3][4] have emerged as versatile and environmentally benign substitutes for heavy metal

• presence of the neighboring tert-butyl group. This method could potentially be extended to other sulfinate salts, particularly aromatic or vinylic species in which the intermediate sulfonium species would be resonance stabilized. However, most commercially available sulfinates are quite expensive. It was

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

• sodium sulfinates and enamides, applying Rose Bengal as photocatalyst and nitrobenzene as terminal oxidant (Scheme 43) [80]. In general, this procedure is suitable for the cross-coupling of a variety of substituted secondary enamides with alkyl, aryl and heteroaryl sodium sulfinate salts. Tertiary

• enamides could not be reacted with sodium sulfinates to yield the respective products. Wang and co-workers described a new method for the cyclization of phenyl propiolates with sulfinic acids, generating valuable coumarin derivatives in 2015 (Scheme 44) [81]. Visible-light irradiation of Eosin Y allows the

The Shono-type electroorganic oxidation of unfunctionalised amides. Carbon–carbon bond formation via electrogenerated N-acyliminium ions

• Alan M. Jones and
• Craig E. Banks

Beilstein J. Org. Chem. 2014, 10, 3056–3072, doi:10.3762/bjoc.10.323

• sulfinates afforded stable crystalline precursors of N-acyliminium ions that are activated by base [60]. The anodic methoxylation products of unfunctionalised amides can be converted to carbonyl compounds (aldehydes or esters) by treatment with cobaltacene [61] or be used as starting materials for the Morita

Palladium-catalyzed substitution of (coumarinyl)methyl acetates with C-, N-, and S-nucleophiles

• Kalicharan Chattopadhyay,
• Erik Fenster,
• Alexander J. Grenning and
• Jon A. Tunge

Beilstein J. Org. Chem. 2012, 8, 1200–1207, doi:10.3762/bjoc.8.133

• tolerated on the coumarin core. In addition to the above Suzuki couplings, acetoxymethylcoumarins were found to undergo palladium-catalyzed substitution with sulfinates and secondary amines under the previously developed palladium-catalysis conditions (Scheme 4). Importantly, related aminomethylcoumarins

• have been shown to have significant biological activity [6][7][8][9][10][11][12][13][14][15]. Regarding the coupling reaction between aryl sulfinates and the coumarinyl acetate, the reaction could be performed without the addition of an external base, since the aryl sulfinate is administered as its

• anion (Scheme 5). Phenyl (4a–c) and tolyl (4d–e) sulfinates were viable coupling partners, giving the product sulfones in good yield. As previously noted, the coumarin core tolerated various simple electronic (4b,c,e) and alkyl (4a,c,d) substitution patterns. Since (coumarinyl)methylamines are known to

Asymmetric synthesis of tertiary thiols and thioethers

• Jonathan Clayden and
• Paul MacLellan

Beilstein J. Org. Chem. 2011, 7, 582–595, doi:10.3762/bjoc.7.68

• classes of organic sulfur compounds, with chirality residing at sulfur, at carbon, or at both [2][3][4][5][6][7][8]. This field of asymmetric organosulfur chemistry is particularly well developed in connection with sulfur(IV) and sulfur(VI) species with chirality at sulfur – namely sulfoxides, sulfinates

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