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

• result of C–S bond formation, the oxidation state of iodine is reduced from +III to +I, causing the loss of hypervalency. This process is extremely exergonic and provides the driving force for the reaction. Additionally, the alternative mechanism of a direct attack of the thiolate nucleophile on the aryl

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

• ). Mechanistic investigations revealed that AgSCF3 was the active species in the transformation. Keywords: C–H bond functionalization; C–S bond formation; hydrazones; synthetic method; trifluoromethylthiolation; Introduction Fluorinated molecules are of paramount importance [1][2][3][4][5][6][7][8][9][10][11

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

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

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

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

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

[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

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

Applications of organocatalysed visible-light photoredox reactions for medicinal chemistry

• Michael K. Bogdos,
• Emmanuel Pinard and
• John A. Murphy

Beilstein J. Org. Chem. 2018, 14, 2035–2064, doi:10.3762/bjoc.14.179

• compatibility. Hajra et al. have reported the direct C–H thiocyanation of substituted imidazo[1,2-a]pyridines, using ammonium thiocyanate, in combination with Eosin Y under irradiation by blue LEDs (Scheme 9) [52]. This is another photoredox example of C–S bond formation, in this case to a highly versatile

A selective removal of the secondary hydroxy group from ortho-dithioacetal-substituted diarylmethanols

• Anna Czarnecka,
• Emilia Kowalska,
• Agnieszka Bodzioch,
• Joanna Skalik,
• Marek Koprowski,
• Krzysztof Owsianik and
• Piotr Bałczewski

Beilstein J. Org. Chem. 2018, 14, 1229–1237, doi:10.3762/bjoc.14.105

• -coupling reactions of substrates containing an 1,3-dithiane moiety are feasible, like in the case of the 2-arylation of 2-aryl-substituted 1,3-dithianes. However, in the case of 2-benzyl-substituted 1,3-dithianes, a tandem elimination/1,3-dithiane ring opening followed by a Pd-catalyzed C−S bond formation

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

• . Carbon disulfide Formation of 1,3-oxathiolane-2-thiones In 2016, Yadav and co-workers reported a photoredox-catalyzed C–S bond formation with carbon disulfide (CS2) as starting material (Scheme 30) [65]. The reaction of CS2 with styrenes under visible-light irradiation and Eosin Y as organic

Chiral phase-transfer catalysis in the asymmetric α-heterofunctionalization of prochiral nucleophiles

• Johannes Schörgenhumer,
• Maximilian Tiffner and
• Mario Waser

Beilstein J. Org. Chem. 2017, 13, 1753–1769, doi:10.3762/bjoc.13.170

• -ring forming cycloetherifications, which gave a straightforward access to tocopherols with very high selectivities [126]. α-Thioetherifications The catalytic stereoselective C–S bond formation in the α-position of prochiral nucleophiles became the topic of broader interest rather recently [127][128

Transition-metal-catalyzed synthesis of phenols and aryl thiols

• Yajun Liu,
• Shasha Liu and
• Yan Xiao

Beilstein J. Org. Chem. 2017, 13, 589–611, doi:10.3762/bjoc.13.58

• -catalyzed Ullmann-type coupling reaction has emerged as an effective method, allowing the synthesis of phenols and aryl thiols from aryl halides through C–O and C–S bond formation, respectively [5][6][7]. Very recently, the C–H activation has made revolutionary advances in organic synthesis because it

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

• h at 110 °C, has also been reported [52]. As part of our ongoing study on sulfur chemistry, we are interested in the one-pot synthesis of target heterocycles such as the Beaucage reagent and benzothiazole as well as sulfides by using Cu-catalysis to mediate the C–S bond formation. Herein, we report

• acetylation reaction was also observed with 2-iodophenol. In consequence, protected amino and hydroxy groups were required for the copper-mediated C–S bond formation to proceed properly (Table 3, entries 3, 4 and 9). This copper-catalyzed coupling reaction was also applied to heteroaromatic and other

• , versatile, efficient and economically attractive procedure for the synthesis of sulfur heterocycles and a variety of sulfides with good yields. This one-pot methodology involves a cascade of reactions starting with a C–S bond formation by copper catalysis and followed by consecutive acyl transfers

Nano copper oxide catalyzed synthesis of symmetrical diaryl sulfides under ligand free conditions

• K. Harsha Vardhan Reddy,
• V. Prakash Reddy,
• A. Ashwan Kumar,
• G. Kranthi and
• Y.V.D. Nageswar

Beilstein J. Org. Chem. 2011, 7, 886–891, doi:10.3762/bjoc.7.101

• -smelling thiols as the main drawback, which leads to environmental and safety problems. To overcome these problems, Zhou [43] and coworkers recently reported an efficient C–S bond formation by the reaction of potassium thiocyanate and aryl halides in the presence of a copper catalyst and a ligand in

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

• (C–S bond formation). Alternatively, stereoselective alkylation, arylation or acylation of a secondary sulfur-based substrate could generate the quaternary centre (C–C bond formation). Review 1 Carbon–sulfur bond formation 1.1 SN2 displacement of a leaving group Stereospecific nucleophilic attack on

Variations in product in reactions of naphthoquinone with primary amines

• Marjit W. Singh,
• Anirban Karmakar,
• Nilotpal Barooah and
• Jubaraj B. Baruah

Beilstein J. Org. Chem. 2007, 3, No. 10, doi:10.1186/1860-5397-3-10

•  3c). Surprisingly in this reaction the product formed is through C-S bond formation rather than C N-bond formation (Scheme 4). The presence of a few well-separated peaks of the products from the starting materials in the NMR spectra (designated by A) shows the formation of the one product with time

• rings are perpendicular to each other. The C-S bond formation reaction can be extended to other thiols such as thiophenol and 4-methoxythiophenol, 4-bromothiophenol etc. with 1,4-naphthoquinone as well as 1,4-benzoquinone. The difference in the case of reaction of 1,4-benzoquinone with primary amine

• whereas similar reaction of 1,4-napthoquinone leads to C-S bond formation. The advantage of these reactions is mildness and versatility. C-N as well as C-S bond formation can be achieved in quinonic compounds under mild conditions. However, limited mechanistic understanding of the reactions is the