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

• is noteworthy that the use of diphenyl disulfide as a sulfenylating agent was not effective in this protocol. N-(Aryl/alkylthio)phthalimide as an efficient sulfenylating reagent could also react with indoles to produce 3-thioindoles in the presence of 0.5 mol % of MgBr2, as a Lewis acid [68

• form intermediate I with the assistance of the Lewis acid. Intermediate I reduced by Et3SiH 139 to give thiol. Through the reaction of thiol with I, disulfide as a byproduct was formed, and intermediate II was generated by the reaction of I with 138. Product 140 was obtained via direct hydride

Non-noble metal-catalyzed cross-dehydrogenation coupling (CDC) involving ether α-C(sp³)–H to construct C–C bonds

• Hui Yu and
• Feng Xu

Beilstein J. Org. Chem. 2023, 19, 1259–1288, doi:10.3762/bjoc.19.94

• -catalyzed CDC reaction of N-methylaniline with ethers. Fe-catalyzed CDC of C(sp3)–H/C(sp3)–H bonds. Fe-catalyzed hydroalkylation of α,β-unsaturated ketones with ethers. Solvent-free Fe(NO3)3-catalyzed CDC of C(sp3)–H/C(sp2)–H bonds. Alkylation of disulfide compounds to afford tetrasubstituted alkenes. Fe

Enabling artificial photosynthesis systems with molecular recycling: A review of photo- and electrochemical methods for regenerating organic sacrificial electron donors

• Grace A. Lowe

Beilstein J. Org. Chem. 2023, 19, 1198–1215, doi:10.3762/bjoc.19.88

• are being developed in non-aqueous solvents. Amines, disulfide-forming thiolates, and NADH derivatives, such as benzimidazoles and acridines, are used as sacrificial donors. Other families of compounds used in other applications such as non-aqueous RFBs, dye-sensitized solar cells, and LOHCs will also

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

• electrogeneration favor a preassembly with Ar−X that i) upon photoexcitation accesses excited states higher than the first (D1) to bolster reactivity and/or ii) following PET assists in the Ar−X•− fragmentation step. The scope was expanded using triethylphosphite (P(OEt)3), dimethyl disulfide (MeSSMe) and bis

Transition-metal-catalyzed C–H bond activation as a sustainable strategy for the synthesis of fluorinated molecules: an overview

• Louis Monsigny,
• Floriane Doche and
• Tatiana Besset

Beilstein J. Org. Chem. 2023, 19, 448–473, doi:10.3762/bjoc.19.35

• disulfide F3CS–SCF3 were employed (Scheme 2, 10 examples, up to 76% yield). With this approach, derivatives bearing an aromatic part substituted at the para-position with electron-donating substituents (1a,b), halogens (1c) as well as electron-withdrawing groups (1d) were difunctionalized in good yields

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

• acetylacetone (19, Scheme 5c) [39]. As mentioned in the Introduction, the metalation of 1,4-dithianes is quite problematic [12][16]. In the unsaturated 1,4-dithiin series, however, the metalation of the cyclic vinyl-1,2-disulfide moiety is somewhat more feasible. Even though linear vinyl-1,2-disulfides such as

Redox-active molecules as organocatalysts for selective oxidative transformations – an unperceived organocatalysis field

• Elena R. Lopat’eva,
• Igor B. Krylov,
• Dmitry A. Lapshin and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2022, 18, 1672–1695, doi:10.3762/bjoc.18.179

• radical (SPyf, Scheme 24) was proposed as a hydrogen atom abstracting agent for unactivated C–H bonds of alkanes and other CH-reagents [123] (Scheme 24). It was generated by the irradiation of the corresponding disulfide with 400 nm LEDs. In the proposed catalytic cycle tetrafluoropyridinyl thiol HSPyf is

• reoxidized to the disulfide by (NH4)2S2O8. The disulfide (SPyf)2 is also consumed in the thiolation of C-centered radicals affording the SPyf radical and target sulfides, which are in turn useful C-centered radical precursors for photoredox-catalyzed reactions [123]. The high efficiency of the thiolation

Microelectrode arrays, electrosynthesis, and the optimization of signaling on an inert, stable surface

• Kendra Drayton-White,
• Siyue Liu,
• Yu-Chia Chang,
• Sakashi Uppal and
• Kevin D. Moeller

Beilstein J. Org. Chem. 2022, 18, 1488–1498, doi:10.3762/bjoc.18.156

• of a Cu(I) precursor, and then confined to the surface of those electrodes with the use of a solution-phase Cu(II)-mediated disulfide bond-forming reaction using excess substrate in solution. The molecules were placed by individually addressable blocks of electrodes on the array that were each

Synthesis of C6-modified mannose 1-phosphates and evaluation of derived sugar nucleotides against GDP-mannose dehydrogenase

• Sanaz Ahmadipour,
• Alice J. C. Wahart,
• Jonathan P. Dolan,
• Laura Beswick,
• Chris S. Hawes,
• Robert A. Field and
• Gavin J. Miller

Beilstein J. Org. Chem. 2022, 18, 1379–1384, doi:10.3762/bjoc.18.142

• active site thiohemiaminal (amine to imine oxidation) or disulfide formation, respectively. Additionally, C6–Cl derivative 9 could probe cysteine alkylation. Reported herein is our exploration of this synthesis and the evaluation of GDP 6-chloro-6-deoxy-ᴅ-mannose 18 against GMD. Results and Discussion

• modifying C6 [4]. Substrate 18 was known to form a disulfide in solution [10], presumably resulting in the glycosyl-1-phosphate being unable to access the enzyme active site; unfortunately, the addition of higher concentrations of reducing agent (DTT) and solid-supported PPh3 to access the reduced form for

Polymer and small molecule mechanochemistry: closer than ever

• José G. Hernández

Beilstein J. Org. Chem. 2022, 18, 1225–1235, doi:10.3762/bjoc.18.128

• to promote the thermodynamically disfavored SN2 cleavage of an individual protein disulfide bond by poorly nucleophilic organic thiols [21]. On the other hand, as for the connection or correlation between polymer and small molecule mechanochemistry, this Perspective article discusses recent studies

• for the fullerenes to pass through. However, the capsule 5 is sensitive to mechanochemical stress due to the porosity, conformational rigidity, and due to the presence of hydrazone and/or disulfide moieties that act as mechanophores. Therefore, during ball milling, 5 gets partially disintegrated at

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

• directly. To that end, we attempted reactions from aminothiol 8a as well as from the corresponding disulfide, both at room temperature and under MWI. In these experiments, the yield of dimer 11a was in the range of 10–34%. We also tried to enhance the oxidative dimerization using a mild oxidizing agent

Cholyl 1,3,4-oxadiazole hybrid compounds: design, synthesis and antimicrobial assessment

• Anas J. Rasras,
• Mohamed El-Naggar,
• Nesreen A. Safwat and
• Raed A. Al-Qawasmeh

Beilstein J. Org. Chem. 2022, 18, 631–638, doi:10.3762/bjoc.18.63

• available cholic acid, which was converted to its cholyl hydrazide (1) as previously reported by us [21]. The produced cholyl hydrazide 1 was heterocyclized to 1,3,4-oxadiazole-2-thiol 2 in excellent yield (93%), via the treatment with carbon disulfide and trimethylamine in refluxing ethanol (Scheme 1) [33

Menadione: a platform and a target to valuable compounds synthesis

• Acácio S. de Souza,
• Ruan Carlos B. Ribeiro,
• Dora C. S. Costa,
• Fernanda P. Pauli,
• David R. Pinho,
• Matheus G. de Moraes,
• Fernando de C. da Silva,
• Luana da S. M. Forezi and
• Vitor F. Ferreira

Beilstein J. Org. Chem. 2022, 18, 381–419, doi:10.3762/bjoc.18.43

• respective ditellurides, a disulfide and a diselenide (Scheme 27). Recently, Ribeiro and co-workers used menadione as a nucleophile for the synthesis of 3-chloromethylated menadione 84, a key intermediate used to prepare selenium-menadione conjugates 86 [128]. In this work, compound 84 was prepared through

Synthesis and late stage modifications of Cyl derivatives

• Phil Servatius and
• Uli Kazmaier

Beilstein J. Org. Chem. 2022, 18, 174–181, doi:10.3762/bjoc.18.19

• naturally occurring HDAC inhibitors contain sulfur moieties like, e.g., disulfides or thioesters. They seem to lack a zinc-chelating group at first sight, but the disulfide or thioester acts as a prodrug and are reduced/cleaved in vivo to liberate the free thiol, a strong Zn-binding group [24][25]. Results

Peptide stapling by late-stage Suzuki–Miyaura cross-coupling

• Hendrik Gruß,
• Rebecca C. Feiner,
• Ridhiwan Mseya,
• David C. Schröder,
• Michał Jewgiński,
• Kristian M. Müller,
• Rafał Latajka,
• Antoine Marion and
• Norbert Sewald

Beilstein J. Org. Chem. 2022, 18, 1–12, doi:10.3762/bjoc.18.1

• ], disulfide- [13], thioether- [14][15][16][17][18][19][20], triazole- [21][22], oxime- [23] and hydrazone formation [24] as well as multicomponent reactions such as the Ugi- or Petasis reaction [25][26][27][28][29][30][31][32]. The content of helicity can moreover be changed by the introduction of a photo

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

• for accessing bis(indolyl)sulfides. To synthesize the unsymmetrical bis(indolyl)sulfide 88, Janosik reacted the indole disulfide 87 with free indole and obtained the product 88 in 81% yield, where the sulfur linkages were 2,3’- with respect to the two indole nuclei (Scheme 11a) [73][74][75][76]. Hall

• compounds having semiconductor properties [80]. The syntheses of these compounds were studied by Janosik in 2006. The N-silyl-protected 3-bromoindole 93 was subjected to strong basic medium (t-BuLi) at low temperature and then quenched with either bis(phenylsulfonyl)sulfide (83) or indole disulfide 94

• the sulfur species 102 takes place to generate copper sulfide complex 103. An oxidative homocoupling gives the bis(indol-3-yl)sulfide 101. Simultaneously, an oxidative homocoupling of the copper sulfide complex can take place to afford disulfide 104, that reacts with N-methylindole again under

Natural products in the predatory defence of the filamentous fungal pathogen Aspergillus fumigatus

• Jana M. Boysen,
• Nauman Saeed and
• Falk Hillmann

Beilstein J. Org. Chem. 2021, 17, 1814–1827, doi:10.3762/bjoc.17.124

• , temperature and aeration, are known to regulate gliotoxin biosynthesis [115][119][120]. The biological activity of ETP’s like gliotoxin is mediated by the active disulfide bridge that targets vulnerable thiols or catalyses oxidative burst formation via redox cycling [78]. In previous studies, these cytotoxic

Chemical approaches to discover the full potential of peptide nucleic acids in biomedical applications

• Nikita Brodyagin,
• Martins Katkevics,
• Venubabu Kotikam,
• Christopher A. Ryan and
• Eriks Rozners

Beilstein J. Org. Chem. 2021, 17, 1641–1688, doi:10.3762/bjoc.17.116

• disulfide linkages to transportan and penetratin peptides. The PNA–peptide conjugates were effectively internalized in human Bowes melanoma cells and in vivo in rats [171]. Transportan peptide localized the PNA in membranous structures of cells, while the penetratin conjugate preferred nuclear localization

A recent overview on the synthesis of 1,4,5-trisubstituted 1,2,3-triazoles

• Pezhman Shiri,
• Ali Mohammad Amani and
• Thomas Mayer-Gall

Beilstein J. Org. Chem. 2021, 17, 1600–1628, doi:10.3762/bjoc.17.114

• disulfide (97) was reported by Xu et al. The reaction has been achieved using a catalytic amount of CuI, LiOt-Bu, and 4 Å molecular sieves in THF as solvent at 40 °C under N2 atmosphere for 12 h and proceeds via a multicomponent CuAAC/persulfuration sequence. The strategy features a wide substrate scope

• ) [55]. A probable mechanism for this transformation was proposed as illustrated in Scheme 29. The cycloaddition reaction between copper(I) acetylide 99 and organic azide 95 occurs to obtain the triazole cuprate intermediate 100, which reacts as a nucleophile with the disulfide electrophile 97 to

• produce the corresponding triazole disulfide 98 [55]. A convenient route to triazole-fused sultams 104 was reported by Latyshev et al. It comprises a modified CuIAAC cycloaddition to produce intermediate sulfonamide-tethered 5-iodo-1,2,3-triazoles 103, followed by a base-mediated cyclization under

Double-headed nucleosides: Synthesis and applications

• Vineet Verma,
• Jyotirmoy Maity,
• Vipin K. Maikhuri,
• Ritika Sharma,
• Himal K. Ganguly and
• Ashok K. Prasad

Beilstein J. Org. Chem. 2021, 17, 1392–1439, doi:10.3762/bjoc.17.98

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

• step without any transition-metal catalyst, ligand, or photocatalyst, this method possesses a splendid application prospect. The reaction mechanism is as follows (Scheme 48): Firstly, carbon disulfide combines with N-methylaniline (134) in the presence of Cs2CO3 to form thiolate 136. Thiolate 136 is

[2 + 1] Cycloaddition reactions of fullerene C₆₀ based on diazo compounds

• Yuliya N. Biglova

Beilstein J. Org. Chem. 2021, 17, 630–670, doi:10.3762/bjoc.17.55

• soluble in the majority of organic solvents and only partially soluble in carbon disulfide, which is expected to ultimately lead to similar insoluble hard-to-recover polymers. It is believed [95] that the best solution to the problem seems to involve the incorporation of solubilizing groups into the

Valorisation of plastic waste via metal-catalysed depolymerisation

• Francesca Liguori,
• Carmen Moreno-Marrodán and
• Pierluigi Barbaro

Beilstein J. Org. Chem. 2021, 17, 589–621, doi:10.3762/bjoc.17.53

• Polystyrene (PS): PS is a low-cost, hard and brittle plastic used both as a solid or foam in protective packaging, containers and trays [151]. It is a nonbiodegradable material accounting for about 10% of municipal solid waste [135]. It is soluble in benzene, carbon disulfide, chlorinated hydrocarbons, lower

Breakdown of 3-(allylsulfonio)propanoates in bacteria from the Roseobacter group yields garlic oil constituents

• Anuj Kumar Chhalodia and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2021, 17, 569–580, doi:10.3762/bjoc.17.51

• structures of the garlic oil constituents and also of the allyl group remained unknown, but its formula was correctly assigned as C3H5. Five decades later, Semmler reported on the nature of allyl propyl disulfide (1), diallyl disulfide (2), diallyl trisulfide (3), and diallyl tetrasulfide (4) from garlic oil

• (Scheme 1A) [2]. The antibacterial principle in garlic was identified in 1944 by Cavallito et al. as allicin (5) [3], a formal oxidation product of disulfide 2. Not only 5, but also several other sulfur compounds from garlic are today known to exhibit diverse biological activities, including inter alia

• labelling into dimethyl disulfide (DMDS), the oxidative dimerization product from MeSH, showing the activity of the demethylation pathway in these bacteria. However, knockout of the dmdA gene in R. pomeroyi still gave a low incorporation of labelling into DMDS, suggesting the presence of another gene

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

• of blue LEDs, allyl boronate 1a (0.1 mmol), disulfide 2a (1.0 equiv) and N-(trifluoromethylthio)phthalimide (Phth-SCF3, 3, 1.5 equiv), the desired trifluoromethylthiolated product 4a was obtained in 71% yield with 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN, 2 mol %) as the

• unactivated alkenes to give the intermediate B. The subsequent addition of B to disulfide 2 affords the difunctionalized products 4 or 5 and the thiophenyl radical C [52]. Finally, the oxidation of radical C by 4CzIPN+ closes the catalytic cycle [53]. Conclusion In summary, we described a visible-light