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

• organosulfur chemistry, sulfenylating agents are an important key in C–S bond formation strategies. Among various organosulfur precursors, N-sulfenylsuccinimide/phthalimide derivatives have shown highly electrophilic reactivity for the asymmetric synthesis of many organic compounds. Hence, in this review

• functional materials and indispensable synthetic intermediates in drug discovery [31][32][33]. Because of their value, constructing C–S bonds has attracted significant attention via metal-catalyzed cross-coupling reactions and metal-free C–S bond formation [34][35][36][37]. Direct sulfenylation of the C–H

• field of organic synthesis. These compounds are readily accessible, safe, and more stable than toxic, unstable, and foul-smelling thiols. These electrophilic sulfur sources have deserved particular interest for the C–S bond formation via the reaction with various nucleophiles. Their preparation is

Exploring the role of halogen bonding in iodonium ylides: insights into unexpected reactivity and reaction control

• Carlee A. Montgomery and
• Graham K. Murphy

Beilstein J. Org. Chem. 2023, 19, 1171–1190, doi:10.3762/bjoc.19.86

• σ-holes might enhance the reaction’s chemoselectivity. Specifically, they investigated the coupling reactions between diazonium and iodonium ylides and the soft Lewis base thioamide 67 [145], intending to achieve C–S bond formation with the β-dicarbonyl, producing 68 (Scheme 16). They compared a

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

•  11). The fact that lithiated 2 is more stable than its more unsaturated counterpart derived from dithiin 3, can possibly be related to stereoelectronic ground state effects in 3 (Figure 2), wherein the non-planar geometry of the nonaromatic ring system can already line up the breaking (C–S) bond with

Palladium-catalyzed solid-state borylation of aryl halides using mechanochemistry

• Koji Kubota,
• Emiru Baba,
• Tamae Seo,
• Tatsuo Ishiyama and
• Hajime Ito

Beilstein J. Org. Chem. 2022, 18, 855–862, doi:10.3762/bjoc.18.86

• transformations. Thus far, mechanochemical palladium-catalyzed cross-coupling reactions such as Suzuki–Miyaura [34][35][36][37][38][39][40][41][42][43][44][45][46][47], Buchwald–Hartwig [48][49][50][51][52], Sonogashira [53][54][55][56], Negishi [57], Mizoroki–Heck [58][59][60], and C–S bond-forming [61

New efficient synthesis of polysubstituted 3,4-dihydroquinazolines and 4H-3,1-benzothiazines through a Passerini/Staudinger/aza-Wittig/addition/nucleophilic substitution sequence

• Long Zhao,
• Mao-Lin Yang,
• Min Liu and
• Ming-Wu Ding

Beilstein J. Org. Chem. 2022, 18, 286–292, doi:10.3762/bjoc.18.32

• protocol towards the synthesis of 4H-3,1-benzothiazines was established by using a P(NMe2)3-mediated C–N/C–S bond formation reaction of 2-aminobenzyl alcohol with isothiocyanates under aerobic conditions [21]. Despite of the above achievements, the development of new efficient methods for the synthesis of

Selective sulfonylation and isonitrilation of para-quinone methides employing TosMIC as a source of sulfonyl group or isonitrile group

• Chuanhua Qu,
• Run Huang,
• Yong Li,
• Tong Liu,
• Yuan Chen and
• Guiting Song

Beilstein J. Org. Chem. 2021, 17, 2822–2831, doi:10.3762/bjoc.17.193

• sulfones is a valuable and appealing task in synthetic chemistry. Traditionally, diarylmethyl sulfones are synthesized by transition-metal-catalyzed deoxy C–S bond-coupling reaction of sodium arylsulfinates with diarylmethanols [11], C–H functionalization of alkyl sulfones with aryl halides [12], and via a

• standard conditions, the desired products 3b or 4b were obtained with yields of 92% and 88%, respectively. Second, the sulfonylated diarylmethane 3b obtained through the C–S bond-cleavage sulfonylation reaction is a versatile building block for preparing diarylmethane derivatives through a nucleophilic

• acids via a triphenylphosphine-mediated deoxygenation process, followed by reaction with sulfonylated diarylmethane 3b to obtain diarylmethane ketone derivatives 6 and 7 [53]. To gain mechanistic insight into this C–S-bond cleavage sulfonylation reaction, some control experiments were conducted (Scheme

A straightforward conversion of 1,4-quinones into polycyclic pyrazoles via [3 + 2]-cycloaddition with fluorinated nitrile imines

• Greta Utecht-Jarzyńska,
• Karolina Nagła,
• Grzegorz Mlostoń,
• Heinz Heimgartner,
• Marcin Palusiak and
• Marcin Jasiński

Beilstein J. Org. Chem. 2021, 17, 1509–1517, doi:10.3762/bjoc.17.108

• -thiadiazoles as the products of [3 + 2]-cycloaddition to the C=S bond [25]. Taking into account that fluorinated heterocycles [31][32][33][34], including pyrazoles [31][35][36], are of great significance for various medicinal and agricultural applications, the development of new methods for the construction of

Synthetic reactions driven by electron-donor–acceptor (EDA) complexes

• Zhonglie Yang,
• Yutong Liu,
• Kun Cao,
• Xiaobin Zhang,
• Hezhong Jiang and
• Jiahong Li

Beilstein J. Org. Chem. 2021, 17, 771–799, doi:10.3762/bjoc.17.67

• construction of C–S bonds C–S bonds are commonly present in amino acids, proteins, glycosides, nucleic acids, and other biological macromolecules. In recent years, photocatalyst- and transition-metal strategies have been employed to construct C–S bonds [66][67][68][69]. The C–S bond synthesis via EDA-complex

Amino- and polyaminophthalazin-1(2H)-ones: synthesis, coordination properties, and biological activity

• Zbigniew Malinowski,
• Emilia Fornal,
• Agata Sumara,
• Renata Kontek,
• Karol Bukowski,
• Beata Pasternak,
• Dariusz Sroczyński,
• Joachim Kusz,
• Magdalena Małecka and
• Monika Nowak

Beilstein J. Org. Chem. 2021, 17, 558–568, doi:10.3762/bjoc.17.50

• . Previously, we have observed that the coupling system involving Xantphos/Pd(OAc)2 (used in the ratio of 15 mol %/15 mol % or 30 mol %/30 mol %) and t-BuOK or DIPEA in 1,4-dioxane as the solvent was effective for the C–N or C–S bond formation [30][31][35]. Unfortunately, it turned out, that the application of

Metal-free visible-light-enabled vicinal trifluoromethyl dithiolation of unactivated alkenes

• Xiaojuan Li,
• Qiang Zhang,
• Weigang Zhang,
• Jinzhu Ma,
• Yi Wang and
• Yi Pan

Beilstein J. Org. Chem. 2021, 17, 551–557, doi:10.3762/bjoc.17.49

• -Markovnikov hydrotrifluoromethylthiolation of alkenes utilizing trifluoromethanesulfonic anhydride (Tf2O) as a radical trifluoromethylthiolating reagent through a deoxygenative reduction and a photoredox radical pathway (Scheme 1b). The C–S bond [44][45] is an important structural motif that is widely present

The synthesis of chiral β-naphthyl-β-sulfanyl ketones via enantioselective sulfa-Michael reaction in the presence of a bifunctional cinchona/sulfonamide organocatalyst

• Deniz Tözendemir and
• Cihangir Tanyeli

Beilstein J. Org. Chem. 2021, 17, 494–503, doi:10.3762/bjoc.17.43

• -Michael addition (SMA) reactions remain a rather less explored reaction among asymmetric organocatalytic transformations, mainly because of the high nucleophilicity of thiols causing difficulties in controlling the stereoselectivity [21], despite C–S bond-forming reactions are of great interest in

Annulation of a 1,3-dithiole ring to a sterically hindered o-quinone core. Novel ditopic redox-active ligands

• Sergey V. Norkov,
• Anton V. Cherkasov,
• Andrey S. Shavyrin,
• Maxim V. Arsenyev,
• Viacheslav A. Kuropatov and
• Vladimir K. Cherkasov

Beilstein J. Org. Chem. 2021, 17, 273–282, doi:10.3762/bjoc.17.26

• -quinone with annulated dithiete ring [18]. Due to the ring-strain of the four-membered cycle the bond distance S(1)–C(11) in thiete (1.866(3) Å) is elongated compared to a standard C–S bond lengths in five-membered cycles (≈1.75 Å). The measured value of the C–S–C angle in this ring is 77.4(2)°. Very

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

• File 1. Conclusion In conclusion, we developed simple, efficient, and selective methods for the synthesis of α-thio esters and α-thio ketones through NaOH-mediated C–S bond formation, followed by C–C bond cleavage. A broad range of β-keto esters and sodium S-organyl sulfurothioates were used as

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

• HFTA and imidazole. In this case, the reaction can proceed through the attack of a nitrogen atom of the imidazole ring at the carbon atom of the C=S bond, leading to the formation of the zwitterion B (Scheme 6). The transfer of a proton from the nitrogen atom to the sulfur atom leads to the formation

• of thiol C, which can lose sulfur, giving rise to the final product. Because of the unsymmetrical nature of substrate A, the attack on the C=S bond of HFTA proceeds by either nitrogen atom of the imidazole ring, resulting in the formation of two isomers for compounds 2–4 and 7. The highly selective

Natural dolomitic limestone-catalyzed synthesis of benzimidazoles, dihydropyrimidinones, and highly substituted pyridines under ultrasound irradiation

• Kumar Godugu,
• Venkata Divya Sri Yadala,
• Mohammad Khaja Mohinuddin Pinjari,
• Trivikram Reddy Gundala,
• Lakshmi Reddy Sanapareddy and
• Chinna Gangi Reddy Nallagondu

Beilstein J. Org. Chem. 2020, 16, 1881–1900, doi:10.3762/bjoc.16.156

• pyridines via C–N, C–C, and C–S bond formations in a mixture of ethanol and H2O under ultrasound irradiation. The catalyst is characterized by XRD, FTIR, Raman spectroscopy, SEM, and EDAX analysis. The main advantages of this methodology include the wide substrate scope, cleaner reaction profile, short

• irradiation (USI). In this paper, we wish to report the use of NDL as a heterogeneous green catalyst for the synthesis of the 1,2-disubstituted benzimidazoles 3, the dihydropyrimidinones/-thiones 7, and the 2-amino-4-(hetero)aryl-3,5-dicarbonitrile-6-sulfanylpyridines 11 via C–N, C–C, and C–S bond-forming

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

• )phenanthridines via C–S bond formation. A typical case is shown in Scheme 16, path b. The process was initiated by the reduction of tosyl chloride (Ts–Cl) by a RuII-based photocatalyst. The resulting sulfonyl radical afforded phenanthridine 16.3b in a very good yield [83]. A related sulfonylation process was

One-pot synthesis of 1,3,5-triazine-2,4-dithione derivatives via three-component reactions

• Gui-Feng Kang and
• Gang Zhang

Beilstein J. Org. Chem. 2020, 16, 1447–1455, doi:10.3762/bjoc.16.120

• chemistry demands. Several methods were reported for the synthesis of triazinethione analogs. One of the most popular methods involved the reaction of a carboximidamide [16], or urea [17] with isothiocyanates. The C=S bond in the latter is highly polar, with the carbon atom always positive and therefore

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

Aldehydes as powerful initiators for photochemical transformations

• Maria A. Theodoropoulou,
• Nikolaos F. Nikitas and
• Christoforos G. Kokotos

Beilstein J. Org. Chem. 2020, 16, 833–857, doi:10.3762/bjoc.16.76

• homolytic cleavage of the C–S bond, providing the sulfonyl radical 186. The sulfonyl radical 186 can then approach anti to the oxazolidinone moiety in 180, generating a β-sulfonyl radical 187, which, once trapped by another sulfonyl cyanide molecule 181, affords the desired product 182, and the sulfonyl

[1,3]/[1,4]-Sulfur atom migration in β-hydroxyalkylphosphine sulfides

• Katarzyna Włodarczyk,
• Piotr Borowski and
• Marek Stankevič

Beilstein J. Org. Chem. 2020, 16, 88–105, doi:10.3762/bjoc.16.11

• activation energy (31.0 kcal/mol), which was followed by slight stabilization of the formed γ-carbanion (−6.1 kcal/mol). The latter should then undergo intramolecular C–S bond formation, followed by hydrolysis, finally leading to the rearranged product. It was then decided to investigate the

Synthesis of novel sulfide-based cyclic peptidomimetic analogues to solonamides

• José Brango-Vanegas,
• Luan A. Martinho,
• Lucinda J. Bessa,
• Andreanne G. Vasconcelos,
• Alexandra Plácido,
• Alex L. Pereira,
• José R. S. A. Leite and
• Angelo H. L. Machado

Beilstein J. Org. Chem. 2019, 15, 2544–2551, doi:10.3762/bjoc.15.247

• new C–S bond. The configuration of the double bond could be assigned as Z for all compounds due to the 1H,1H-NOESY correlations between the C3 hydrogen and the NH hydrogen of the amino acid residue attached to the adduct residue. The IR spectra of analogues 9 were quite similar (Supporting Information

Recent advances on the transition-metal-catalyzed synthesis of imidazopyridines: an updated coverage

• Gagandeep Kour Reen,
• Ashok Kumar and
• Pratibha Sharma

Beilstein J. Org. Chem. 2019, 15, 1612–1704, doi:10.3762/bjoc.15.165

Multicomponent reactions (MCRs): a useful access to the synthesis of benzo-fused γ-lactams

• Edorta Martínez de Marigorta,
• Jesús M. de Los Santos,
• Ana M. Ochoa de Retana,
• Javier Vicario and
• Francisco Palacios

Beilstein J. Org. Chem. 2019, 15, 1065–1085, doi:10.3762/bjoc.15.104

• with the nucleophilic aromatic ring in a Friedel–Crafts alkylation process, thus incorporating the carbon atom in a formal C(sp2)–H/C(sp3)–H cross-dehydrogenative coupling. Finally, an oxidation of sulfide 7 to sulfoxide 8 and the subsequent attack of amide 2 with cleavage of the C–S bond and formation

Degenerative xanthate transfer to olefins under visible-light photocatalysis

• Atsushi Kaga,
• Xiangyang Wu,
• Joel Yi Jie Lim,
• Hirohito Hayashi,
• Yunpeng Lu,
• Edwin K. L. Yeow and
• Shunsuke Chiba

Beilstein J. Org. Chem. 2018, 14, 3047–3058, doi:10.3762/bjoc.14.283

• previously been ascribed to the absorption of the xanthic acid radical formed plausibly from homolytic C–S bond cleavage of the short-lived triplet state of xanthate 1a [22]. The ns-TA spectra of photocatalyst 8 (25 μM) in the presence of xanthate 1a (40 mM) in degassed DMSO at various delay times are shown

• absorption spectroscopy study of xanthate 1a was conducted (Figure 3). The UV–vis absorption spectrum of 1a (1 mM in DMSO) showed absorption bands at 340–390 nm assigned to the n→π* electronic transition of the C=S bond as a characteristic peak of thiocarbonyl containing compounds [56]. In fact, the reaction

• of 1a and 2a under 365 nm UV lamp irradiation without a photocatalyst delivered product 3aa in 75% yield (Table 1, entry 9). This indicates the excitation of xanthate 1a through an n→π* electronic transition of the C=S bond is in operation in the UV irradiation process. The involvement of a radical

Synthesis of aryl sulfides via radical–radical cross coupling of electron-rich arenes using visible light photoredox catalysis

• Amrita Das,
• Mitasree Maity,
• Simon Malcherek,
• Burkhard König and
• Julia Rehbein

Beilstein J. Org. Chem. 2018, 14, 2520–2528, doi:10.3762/bjoc.14.228

• , antidepressant or antileukotriene agents (Figure 1). Three of the five most selling drugs in 2015 were organosulfur compounds. The majority of methods for C–S bond synthesis use transition metal-catalyzed cross coupling of thiols and their derivatives with organohalides [4][5][6], arylboronic acids [7], aryl