Development of N-F fluorinating agents and their fluorinations: Historical perspective

• Teruo Umemoto,
• Yuhao Yang and
• Gerald B. Hammond

Beilstein J. Org. Chem. 2021, 17, 1752–1813, doi:10.3762/bjoc.17.123

• reactivity than the sulfonamide reagents such as Barnette’s N-fluoro-N-alkylarenesulfonamides, since the electronic density on the nitrogen was greatly decreased by two strong electron-withdrawing CF3SO2 groups. Reagent 7-1a reacted slowly with benzene and toluene under neat conditions, whereas activated

• pentafluoropyridine, the precursor 11-1 was prepared as illustrated in Scheme 25. Treatment of 11-1 with neat F2 in acetonitrile at −10 °C under reduced pressure gave N-fluoro-sulfonamide 11-2 in 89% yield. This product was however a 9:1 mixture of the N-F reagent 11-2 and the protonated compound of 11-1. The

• -rich substrates such as sodium diethyl (phenyl)malonate, 1-morpholinocyclohexene, phenol, and anisole (Scheme 47). The fluorination power of the carboxamide 21-2 was less than that of its N-F sulfonamide analog 11-2. 1-22. N,N’-Difluoro-1,4-diazoniabicyclo[2.2.2]octane salts In 1996, Umemoto and co

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

• 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

• )amine (TTTA) as ligand, and THF as solvent at 50 °C. The obtained sulfonamide-tethered 5-iodo-1,2,3-triazoles 103 were then cyclized upon heating in the presence of Cs2CO3 to give triazole-fused sultams 104. A good to excellent yield of sultam derivatives 104 containing aryl and alkyl substituents on

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

N-tert-Butanesulfinyl imines in the asymmetric synthesis of nitrogen-containing heterocycles

• Joseane A. Mendes,
• Paulo R. R. Costa,
• Miguel Yus,
• Francisco Foubelo and
• Camilla D. Buarque

Beilstein J. Org. Chem. 2021, 17, 1096–1140, doi:10.3762/bjoc.17.86

• carried out in the presence of the electrophile (chiral imine 79). Surprisingly, both diastereomeric aldimines 79 (RS and SS) gave similar results concerning the stereochemical outcome, suggesting that the chiral sulfonamide moiety was not involved in the stereocontrol during this tandem Barbier addition

• proceeded with high levels of diastereocontrol. The resulting sulfonamide derivatives 95 were transformed into the target spiro compound 97 by performing successive desulfinylation and intramolecular palladium-catalyzed N-arylation. To rationalize the stereochemical course of the addition, DFT calculations

Beyond ribose and phosphate: Selected nucleic acid modifications for structure–function investigations and therapeutic applications

• Christopher Liczner,
• Kieran Duke,
• Gabrielle Juneau,
• Martin Egli and
• Christopher J. Wilds

Beilstein J. Org. Chem. 2021, 17, 908–931, doi:10.3762/bjoc.17.76

• overall steps [164]. ASOs containing these modified nucleosides have demonstrated promising antitumor activity for lymphoma and lung cancer [165]. Numerous other LNA analogues have been constructed including, but not limited to, 2'-N-guanidino,4'-C-ethylene (GENA) (Figure 7I) [166], sulfonamide-bridged

DNA with zwitterionic and negatively charged phosphate modifications: Formation of DNA triplexes, duplexes and cell uptake studies

• Yongdong Su,
• Maitsetseg Bayarjargal,
• Tracy K. Hale and
• Vyacheslav V. Filichev

Beilstein J. Org. Chem. 2021, 17, 749–761, doi:10.3762/bjoc.17.65

• [47][48], a sugar [49][50], or the DNA backbone [51][52][53] leading to the formation of more stable duplexes and triplexes [54]. The introduction of sulfonamide RNA (SaRNA monomers) to replace the phosphodiester backbone led to charge-neutral sulfonamide antisense oligonucleotides (SaASOs), which

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

• respect, a bifunctional quinine-derived sulfonamide organocatalyst was developed to catalyze the asymmetric sulfa-Michael reaction of naphthalene-1-thiol with trans-chalcone derivatives. The target sulfa-Michael adducts were obtained with up to 96% ee under mild conditions and with a low (1 mol

• building blocks for the construction of more elaborate structures [7][8][9][10][11]. An outstanding class of quinine derived organocatalysts exhibits a bifunctional mode of activation by the incorporation of an acidic unit, such as urea, thiourea, squaramide or sulfonamide moieties, giving rise to the

• sulfa-Michael additions of thiols to chalcones with sulfonamide-type organocatalysts in the literature [30][31], in this study, a new quinine sulfonamide organocatalyst derivative was developed to catalyze the enantioselective SMA of naphthalene-1-thiol to trans-chalcones under mild conditions and with

Chiral anion recognition using calix[4]arene-based ureido receptors in a 1,3-alternate conformation

• Tereza Horáčková,
• Jan Budka,
• Vaclav Eigner,
• Wen-Sheng Chung,
• Petra Cuřínová and
• Pavel Lhoták

Beilstein J. Org. Chem. 2020, 16, 2999–3007, doi:10.3762/bjoc.16.249

• . The shapes and geometries of anions are widely different, and therefore the design of corresponding tailor-made receptors is based mostly on more directional interactions, such as hydrogen bonds. Indeed, an incredible number of neutral receptors bearing amide, sulfonamide, urea, thiourea, pyrrole, or

Regioselective synthesis of heterocyclic N-sulfonyl amidines from heteroaromatic thioamides and sulfonyl azides

• Vladimir Ilkin,
• Vera Berseneva,
• Tetyana Beryozkina,
• Tatiana Glukhareva,
• Lidia Dianova,
• Wim Dehaen,
• Eugenia Seliverstova and
• Vasiliy Bakulev

Beilstein J. Org. Chem. 2020, 16, 2937–2947, doi:10.3762/bjoc.16.243

• Beckmann reaction of oximes with p-toluenesulfonyl azide [34], the sulfonyl ynamide rearrangement by treatment with amines [35], the sodium iodide catalyzed reaction of sulfonamide with formamide [36], and the condensation of sulfonamide derivatives with DMF–DMA [37]. A few representatives of N-sulfonyl

Three-component reactions of aromatic amines, 1,3-dicarbonyl compounds, and α-bromoacetaldehyde acetal to access N-(hetero)aryl-4,5-unsubstituted pyrroles

• Wenbo Huang,
• Kaimei Wang,
• Ping Liu,
• Minghao Li,
• Shaoyong Ke and
• Yanlong Gu

Beilstein J. Org. Chem. 2020, 16, 2920–2928, doi:10.3762/bjoc.16.241

• to access the insect-growth regulators [44]. It is noteworthy that the sulfonamide group persisted during this transformation, and the desired pyrrole product 4r could be obtained in 69% yield. A high yield was also obtained when the phenyl group was replaced with a naphthyl group in 4s. Subsequently

A complementary approach to conjugated N-acyliminium formation through photoredox-catalyzed intermolecular radical addition to allenamides and allencarbamates

• Olusesan K. Koleoso,
• Matthew Turner,
• Felix Plasser and
• Marc C. Kimber

Beilstein J. Org. Chem. 2020, 16, 1983–1990, doi:10.3762/bjoc.16.165

• product, with only a complex mixture, as identified by 1H NMR, being isolated. Significantly, in the 1H NMR spectra of this complex mixture we observed complete fragmentation of the sulfonamide unit. Two chiral allenamides (24 and 25) were exposed to the photoredox conditions with 2,4-dimethylaniline, and

Pauson–Khand reaction of fluorinated compounds

• Jorge Escorihuela,
• Daniel M. Sedgwick,
• Alberto Llobat,
• Mercedes Medio-Simón,
• Pablo Barrio and
• Santos Fustero

Beilstein J. Org. Chem. 2020, 16, 1662–1682, doi:10.3762/bjoc.16.138

• ). The cyclization of internal alkyne substrate 24b yielded pyrrolidine ring-fused cyclopentenone 25b in similar yield but lower diastereoselectivity. Finally, N-propargyl-N-[2-(trifluoromethyl)allyl] ether 24d, containing an ether linkage instead of the aforementioned sulfonamide linkage, gave furan

Fluorinated phenylalanines: synthesis and pharmaceutical applications

• Laila F. Awad and
• Mohammed Salah Ayoup

Beilstein J. Org. Chem. 2020, 16, 1022–1050, doi:10.3762/bjoc.16.91

• and 12b afforded ʟ-4-[sulfono(difluoromethyl)]phenylalanine derivatives 13a and 13b, respectively [39] (Scheme 3). 1.2. Alkylations of fluorinated aryl halides with a chiral auxiliary Alternatively, the coupling of the bis(dimethoxybenzyl)-protected sulfonamide 14, instead of the esters 10a and 10b

Recent advances in Cu-catalyzed C(sp³)–Si and C(sp³)–B bond formation

• Balaram S. Takale,
• Ruchita R. Thakore,
• Elham Etemadi-Davan and
• Bruce H. Lipshutz

Beilstein J. Org. Chem. 2020, 16, 691–737, doi:10.3762/bjoc.16.67

• aldimines 62, failing to use unactivated educts [40]. Likewise, the α-silylated sulfonamide 67 was obtained in modest ee, although the chemical yield of the transformation was very low (15%). Changing the protecting group from Ts to methyl (68) or Boc (70) in the aldimine series did not alter yields or ees

Aerobic synthesis of N-sulfonylamidines mediated by N-heterocyclic carbene copper(I) catalysts

• Faïma Lazreg,
• Marie Vasseur,
• Alexandra M. Z. Slawin and
• Catherine S. J. Cazin

Beilstein J. Org. Chem. 2020, 16, 482–491, doi:10.3762/bjoc.16.43

• ]. Based on these earlier results, the reactivity of these catalysts was investigated in the context of achieving formation of the challenging sulfonamide derivatives. Herein, we report the high efficiency of cationic copper(I) complexes for the formation of N-sulfonylamidines via a three-component

Archangelolide: A sesquiterpene lactone with immunobiological potential from Laserpitium archangelica

• Silvie Rimpelová,
• Michal Jurášek,
• Lucie Peterková,
• Jiří Bejček,
• Vojtěch Spiwok,
• Miloš Majdl,
• Michal Jirásko,
• Miloš Buděšínský,
• Juraj Harmatha,
• Eva Kmoníčková,
• Pavel Drašar and
• Tomáš Ruml

Beilstein J. Org. Chem. 2019, 15, 1933–1944, doi:10.3762/bjoc.15.189

• fluorescent 5-(dimethylamino)-N-(prop-2-yn-1-yl)naphthalene-1-sulfonamide (synthesized according to [18]) using CuI and TBTA [19] catalysis. All of the synthesized compounds were thoroughly described by NMR (Supporting Information File 1, Table S1), IR, optical rotation (Supporting Information File 1, section

• . Synthesis of 11-(5-(4-((5-(dimethylamino)naphthalene-1-sulfonamido)methyl)-1H-1,2,3-triazol-1-yl)pentanoylarchangelolide (5) To a solution of azidovalerate 4 (40 mg, 0.063 mmol) and 5-(dimethylamino)-N-(prop-2-yn-1-yl)naphthalene-1-sulfonamide (20 mg, 0.07 mmol) in THF (3 mL), CuI (50 µL of 1 M water

Robust perfluorophenylboronic acid-catalyzed stereoselective synthesis of 2,3-unsaturated O-, C-, N- and S-linked glycosides

• Madhu Babu Tatina,
• Xia Mengxin,
• Rao Peilin and
• Zaher M. A. Judeh

Beilstein J. Org. Chem. 2019, 15, 1275–1280, doi:10.3762/bjoc.15.125

• and trimethyl(propargyl)silane), S-nucleophiles (using thiophenol and p-toluenethiol) and N-nucleophiles (methane sulfonamide and p-toluene sulfonamide) (Figure 1). In all the cases, the reactions successfully gave the respective 2,3-unsaturated glycosides 3a–u in up to 92% yield with mainly α

Targeting the Pseudomonas quinolone signal quorum sensing system for the discovery of novel anti-infective pathoblockers

• Christian Schütz and
• Martin Empting

Beilstein J. Org. Chem. 2018, 14, 2627–2645, doi:10.3762/bjoc.14.241

• mimetics More recently, Ji et al. published two classes of sulfonyladenosine inhibitors, more precisely the sulfamate/sulfamide inhibitors 5–9 and the vinyl sulfonamide inhibitors 10 and 11 (Figure 5). While the latter showed very low affinity for the protein, the former displayed Ki values between 88 nM

Pathoblockers or antivirulence drugs as a new option for the treatment of bacterial infections

• Matthew B. Calvert,
• Varsha R. Jumde and
• Alexander Titz

Beilstein J. Org. Chem. 2018, 14, 2607–2617, doi:10.3762/bjoc.14.239

• , Titz et al. have developed small molecule LecB inhibitors derived from mannose and obtained potent monovalent inhibitors (compound 15) of LecB-mediated bacterial adhesion [47]. The sulfonamide 15 and cinnamide 16 were developed to take advantage of interactions with a nearby shallow pocket, and indeed

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

• . Considering that Ered*(cat/cat•−) is greater than +2 V (vs SCE) for acridinium salts, the limited oxidising power is not the most probable explanation. Instability of the heteroaromatic radical cation seems more plausible. The authors explore both aromatic and heteroaromatic pendant groups on the sulfonamide

Recent advances in hypervalent iodine(III)-catalyzed functionalization of alkenes

• Xiang Li,
• Pinhong Chen and
• Guosheng Liu

Beilstein J. Org. Chem. 2018, 14, 1813–1825, doi:10.3762/bjoc.14.154

• of substrates bearing either two or four methylene groups between the alkene and sulfonamide failed to provide the fluoroheterocycles. Difluorination of alkenes Hara and co-workers reported a vicinal difluorination of unactivated alkenes in the presence of stoichiometric amounts of difluoro

Synthesis of spirocyclic scaffolds using hypervalent iodine reagents

• Fateh V. Singh,
• Priyanka B. Kole,
• Saeesh R. Mangaonkar and
• Samata E. Shetgaonkar

Beilstein J. Org. Chem. 2018, 14, 1778–1805, doi:10.3762/bjoc.14.152

• systems. In 2015, Jain and Ciufolini [124] developed PIDA-mediated spirocyclization of 2-naphtholic sulfonamides 124 to spiropyrrolidine derivatives 125. The spirocyclization reactions were carried out by treating N-sulfonamide substrates 124 with (diacetoxyiodo)benzene (15) in trifluoroacetic acid (TFA

• electrophile. PIDA-mediated spirocyclization of phenolic sulfonamide 122 to spiroketones 123. Iodine(III)-mediated oxidative spirocyclization of 2-naphthol derivatives 124 to spiropyrrolidines 125. PIDA-mediated oxidative spirocyclization of m-substituted phenols 126 to tricyclic spiroketals 127. Iodine(III

Cobalt-catalyzed C–H cyanations: Insights into the reaction mechanism and the role of London dispersion

• Eric Detmar,
• Valentin Müller,
• Daniel Zell,
• Lutz Ackermann and
• Martin Breugst

Beilstein J. Org. Chem. 2018, 14, 1537–1545, doi:10.3762/bjoc.14.130

• the desired transformation. As the calculated rate-limiting transition state TS3 benefits from a stabilization of the developing negative charge on the sulfonamide, the relative rates of Scheme 3 provide further support for the migratory insertion representing the rate determining step [44]. As

Nanoreactors for green catalysis

• M. Teresa De Martino,
• Loai K. E. A. Abdelmohsen,
• Floris P. J. T. Rutjes and
• Jan C. M. van Hest

Beilstein J. Org. Chem. 2018, 14, 716–733, doi:10.3762/bjoc.14.61

• between heteroaryl bromides, chlorides or iodides and carbamate, sulfonamide or urea derivatives to be successfully realized in water using palladium-loaded TPGS-750-M (dl-α-tocopherol methoxypolyethylene glycol succinate) micelles (Scheme 1). Moreover, this micellar catalytic system allowed for catalyst

Synthetic and semi-synthetic approaches to unprotected N-glycan oxazolines

• Antony J. Fairbanks

Beilstein J. Org. Chem. 2018, 14, 416–429, doi:10.3762/bjoc.14.30

• the GlcNAc acceptor has an azide or sulfonamide at position 2, rather than acetamide or N-phthalamide. Scheme 5 shows an example of the synthesis of a modified core N-glycan tetrasaccharide oxazoline from the several reported by Wang [77] using this approach. In this case following formation of the