Mechanisms for radical reactions initiating from N-hydroxyphthalimide esters

• Carlos R. Azpilcueta-Nicolas and
• Jean-Philip Lumb

Beilstein J. Org. Chem. 2024, 20, 346–378, doi:10.3762/bjoc.20.35

• co-workers reported that the combination of NHPI esters and cesium carbonate (Cs2CO3) gave rise to a new absorption band in the visible region, suggesting the formation of a photoactive charge-transfer complex [70]. This activation mode was initially employed in a decarboxylative coupling reaction

• (Scheme 30B). Then, cesium carbonate deprotonates the enol OH in 145, to provide the enolate form of Breslow’s intermediate 146, which is a suitable reducing agent to trigger the fragmentation of NHPI ester 58 (E°ox = −0.97 V vs SCE in MeCN). Hence, it is proposed that enolate 146 induces the single

Aldiminium and 1,2,3-triazolium dithiocarboxylate zwitterions derived from cyclic (alkyl)(amino) and mesoionic carbenes

• Nedra Touj,
• François Mazars,
• Guillermo Zaragoza and
• Lionel Delaude

Beilstein J. Org. Chem. 2023, 19, 1947–1956, doi:10.3762/bjoc.19.145

• . Yet, we did not try to purify them any further. Before closing this section, it should be stressed that we were not able to isolate any dithiocarboxylate betaines when aldiminium salt 3b or triazolium salt 5a were treated with cesium carbonate and carbon disulfide in acetonitrile in the presence of

Consecutive four-component synthesis of trisubstituted 3-iodoindoles by an alkynylation–cyclization–iodination–alkylation sequence

• Nadia Ledermann,
• Alae-Eddine Moubsit and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2023, 19, 1379–1385, doi:10.3762/bjoc.19.99

• alkynyl-substituted 3-iodoindole 6 as product in 42% isolated yield in the sense of a pseudo-five-component reaction (Scheme 3). Finally, the 3-iodoindole 5a and arylboronic acids 7 were employed in a standard Suzuki protocol with cesium carbonate as a base to give rise to the formation of 1,2,3

• , 63.81; H, 3.74; N, 2.96. Synthesis of 1,2,3-trisubstituted indole 8b (typical procedure) 3-Iodoindole 5a (167 mg, 0.50 mmol), (p-tolyl)boronic acid (7b, 204 mg, 1.50 mmol), Pd(PPh3)4 (28.9 mg, 25.0 μmol), and cesium carbonate (652 mg, 2.00 mmol) were placed in an oven-dried Schlenk tube with magnetic

Lewis acid-catalyzed Pudovik reaction–phospha-Brook rearrangement sequence to access phosphoric esters

• Jin Yang,
• Dang-Wei Qian and
• Shang-Dong Yang

Beilstein J. Org. Chem. 2022, 18, 1188–1194, doi:10.3762/bjoc.18.123

• catalyst through a similar transformation under solvent-free conditions [44]. Recently, Zhang’s group disclosed a cesium carbonate-catalyzed Pudovik reaction–phospha-Brook rearrangement sequence and extended the phosphorus source from phosphate to phosphonate [45]. Despite of these important advancements

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

Synthesis of new pyrazolo[1,2,3]triazines by cyclative cleavage of pyrazolyltriazenes

• Nicolai Wippert,
• Martin Nieger,
• Claudine Herlan,
• Nicole Jung and
• Stefan Bräse

Beilstein J. Org. Chem. 2021, 17, 2773–2780, doi:10.3762/bjoc.17.187

• chains to the pyrazole moiety. The addition of several aliphatic bromides or iodides 14 in combination with potassium or cesium carbonate in DMSO gave a mixture of the regioisomeric compounds 12 and 13 due to the addition of the alkyl substituents to one of both pyrazole-nitrogen atoms. As shown in Table

Recent advances in organocatalytic asymmetric aza-Michael reactions of amines and amides

• Pratibha Sharma,
• Raakhi Gupta and
• Raj K. Bansal

Beilstein J. Org. Chem. 2021, 17, 2585–2610, doi:10.3762/bjoc.17.173

• ) in the presence of cesium carbonate and an N-benzylquininium salt as catalyst (cat. 48) (solid–liquid phase-transfer conditions) to give the corresponding adducts in 40–90% yields with excellent ee of up to 99% (Table 10) [44]. A different type of asymmetric aza-Michael addition was developed by Wang

Regioselective N-alkylation of the 1H-indazole scaffold; ring substituent and N-alkylating reagent effects on regioisomeric distribution

• Ryan M. Alam and
• John J. Keating

Beilstein J. Org. Chem. 2021, 17, 1939–1951, doi:10.3762/bjoc.17.127

• effect of varying these reaction parameters, using n-pentyl bromide as the prototypical N-alkylating reagent (Table 1). Early investigations revealed that the combination of cesium carbonate (Cs2CO3) in dimethylformamide (DMF) at room temperature (≈ 20 °C) afforded a mixture of N-1 and N-2 regioisomers

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

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

Total synthesis of decarboxyaltenusin

• Lucas Warmuth,
• Aaron Weiß,
• Marco Reinhardt,
• Anna Meschkov,
• Ute Schepers and
• Joachim Podlech

Beilstein J. Org. Chem. 2021, 17, 224–228, doi:10.3762/bjoc.17.22

• a 73% yield. The Suzuki coupling of boronate 6a and aryl bromide 9a using palladium acetate and cesium carbonate in the presence of the ligand SPhos [25] yielded biaryl 10a with virtually quantitative yield (98%, Scheme 4). Unfortunately, the removal of non-identified byproducts and of 9a (which had

Synthesis of 4-substituted azopyridine-functionalized Ni(II)-porphyrins as molecular spin switches

• Jannis Ludwig,
• Tobias Moje,
• Fynn Röhricht and
• Rainer Herges

Beilstein J. Org. Chem. 2020, 16, 2589–2597, doi:10.3762/bjoc.16.210

• of 1e (top), 1h (left) and 1j (right) in acetone water (1:9) (solid line) and after deprotonation using cesium carbonate (dashed line) in the PSS at 505 nm (green) and 435 nm (blue). Synthesis of the nitroso compounds 3 and 6 using the two different methods described by Wegner et al. [19][20][21] and

Design and synthesis of a bis-macrocyclic host and guests as building blocks for small molecular knots

• Elizabeth A. Margolis,
• Rebecca J. Keyes,
• Stephen D. Lockey IV and
• Edward E. Fenlon

Beilstein J. Org. Chem. 2020, 16, 2314–2321, doi:10.3762/bjoc.16.192

• changing the order of these steps would be beneficial. Alkylation of terephthalate 12 with azido-bromide 6 using cesium carbonate as the base provided high yields (82%) of core diazide 14 (Scheme 3). Click cycloaddition of 14 with an excess of dialkyne 10 also proceeded in high yields (87%) to give diester

Convenient access to pyrrolidin-3-ylphosphonic acids and tetrahydro-2H-pyran-3-ylphosphonates with multiple contiguous stereocenters from nonracemic adducts of a Ni(II)-catalyzed Michael reaction

• Alexander N. Reznikov,
• Dmitry S. Nikerov,
• Anastasiya E. Sibiryakova,
• Victor B. Rybakov,
• Evgeniy V. Golovin and
• Yuri N. Klimochkin

Beilstein J. Org. Chem. 2020, 16, 2073–2079, doi:10.3762/bjoc.16.174

• detected in the reaction even after 72 h in the presence of 1 equiv of potassium phosphate or carbonate with TEBAC (0.1 equiv, Table 1, entries 4 and 5). If potassium fluoride or cesium carbonate were used as a base, the initial phosphonate 6e was consumed in a few hours, but unidentified products were

Reaction of indoles with aromatic fluoromethyl ketones: an efficient synthesis of trifluoromethyl(indolyl)phenylmethanols using K₂CO₃/n-Bu₄PBr in water

• Thanigaimalai Pillaiyar,
• Masoud Sedaghati and
• Gregor Schnakenburg

Beilstein J. Org. Chem. 2020, 16, 778–790, doi:10.3762/bjoc.16.71

• (TMG), also known as Barton's base, in excellent yields (Figure 2A) [24]. Recently, Liu and co-workers reported this reaction in the presence of cesium carbonate in acetonitrile (Figure 2B) [25]. Dinuclear zinc [26], cinchonidine catalysts, and solvent-free conditions [27] have been also utilized for

Synthesis and circularly polarized luminescence properties of BINOL-derived bisbenzofuro[2,3-b:3’,2’-e]pyridines (BBZFPys)

• Ryo Takishima,
• Yuji Nishii,
• Tomoaki Hinoue,
• Yoshitane Imai and
• Masahiro Miura

Beilstein J. Org. Chem. 2020, 16, 325–336, doi:10.3762/bjoc.16.32

• using cesium carbonate as base in DMF at 40 °C [42], giving both the enantiomers of 2 in optically pure forms. The remaining fluorine substituents were subsequently replaced by a series of phenols including unsubstituted phenol, p-tert-butylphenol, and m-tert-butylphenol to produce the corresponding

Synthesis and characterization of bis(4-amino-2-bromo-6-methoxy)azobenzene derivatives

• David Martínez-López,
• Amirhossein Babalhavaeji,
• Diego Sampedro and
• G. Andrew Woolley

Beilstein J. Org. Chem. 2019, 15, 3000–3008, doi:10.3762/bjoc.15.296

• cm × 8 mm). Then, morpholine (84 mg, 0.96 mmol), tris(dibenzylideneacetone)dipalladium(0) (29.3 mg, 0.032 mmol), RuPhos (29.8 mg, 0.064 mmol), and cesium carbonate (302.4 mg, 0.96 mmol) were added. The mixture was heated at 100 ºC in the pressure tube for 24 hours. The reaction progress was monitored

• cesium carbonate (302.4 mg, 0.96 mmol) were added. The mixture was heated at 100 ºC in a pressure tube for 36 hours. The reaction progress was monitored by TLC until the starting reagent was consumed. The solvent was evaporated under reduced pressure, and the resulting oil was extracted with DCM three

A new approach to silicon rhodamines by Suzuki–Miyaura coupling – scope and limitations

• Thines Kanagasundaram,
• Antje Timmermann,
• Carsten S. Kramer and
• Klaus Kopka

Beilstein J. Org. Chem. 2019, 15, 2569–2576, doi:10.3762/bjoc.15.250

• be an effective catalyst for the synthesis of rhodamine and rosamine dyes as well as for their selenium or tellurium analogous [29], the usage of that Pd(0) catalyst showed yields comparable with those obtained with PdCl2(PPh3)2 (Table 1, entry 4). The exchange of sodium carbonate with cesium

• carbonate resulted in no reaction at all (Table 1, entry 5). Whereby usage of potassium phenyltrifluoroborate (19) resulted in a yield comparable to boroxine 18b (Table 1, entry 6), usage of pinacol ester 20 showed no reaction in the cross-coupling reaction (Table 1, entry 7). Although described

Synthesis of benzo[d]imidazo[2,1-b]benzoselenoazoles: Cs₂CO₃-mediated cyclization of 1-(2-bromoaryl)benzimidazoles with selenium

• Mio Matsumura,
• Yuki Kitamura,
• Arisa Yamauchi,
• Yoshitaka Kanazawa,
• Yuki Murata,
• Tadashi Hyodo,
• Kentaro Yamaguchi and
• Shuji Yasuike

Beilstein J. Org. Chem. 2019, 15, 2029–2035, doi:10.3762/bjoc.15.199

• . Keywords: benzimidazole; cesium carbonate; cyclization; selenium; selenoazole; Introduction Selenium-containing heterocyclic ring systems have attracted attention not only because of their chemical properties and reactivities, but also for their wide biological activities [1][2][3][4]. For example

• . Experimental General procedure for the synthesis of benzoimidazo[2,1-b]benzoselenoazoles: 1-(2-Bromoaryl)benzimidazoles 1 (0.5 mmol), selenium powder (79 mg, 1.0 mmol, 2 equiv), and cesium carbonate (326 mg, 1.0 mmol, 2 equiv) were dissolved in DMF (1 mL) under Ar atmosphere. The mixture was stirred at 150 °C

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

• aromatic or aliphatic, only in case of triazoles substituted with an acetate group the final product was obtained in 66% yield. An open-flask, one-pot, Cu(II)-catalyzed ligand-free approach towards C–N bond formation was reported by Rasheed et al. [116]. The reaction was catalyzed by Cu(OAc)2 with cesium

• carbonate as a base under aerobic conditions. Along with the synthesis of pyrido[1,2-a]benzimidazoles 78, they have reported the synthesis of benzimidazo[1,2-a]quinoline 79 and benzimidazo[1,2-a]isoquinoline 80 in good to excellent yields. They have used differently substituted arylboronic acids 77 as one

Synthesis of aryl cyclopropyl sulfides through copper-promoted S-cyclopropylation of thiophenols using cyclopropylboronic acid

• Emeline Benoit,
• Ahmed Fnaiche and
• Alexandre Gagnon

Beilstein J. Org. Chem. 2019, 15, 1162–1171, doi:10.3762/bjoc.15.113

• tolerated, giving a comparable yield as the "standard conditions" (Table 1, entry 8). While changing the inorganic base to potassium phosphate tribasic or potassium carbonate gave yields below 75%, we found that cesium carbonate provided a net increase in the yield of the reaction (Table 1, entry 9

• procedure for the synthesis of aryl cyclopropyl sulfides A sealed tube equipped with a magnetic stirring bar was charged under ambiant air with cyclopropylboronic acid (25, 0.6 mmol, 1.5 equiv), cesium carbonate (0.4 mmol, 1.0 equiv), Cu(OAc)2 (0.4 mmol, 1.0 equiv), 2,2'-bipyridine (0.4 mmol, 1.0 equiv) and

Hypervalent organoiodine compounds: from reagents to valuable building blocks in synthesis

• Gwendal Grelier,
• Benjamin Darses and
• Philippe Dauban

Beilstein J. Org. Chem. 2018, 14, 1508–1528, doi:10.3762/bjoc.14.128

• metal-free alternative to the previous methods of formation of sulfur heterocycles 70 has been reported by using elemental sulfur in the presence of cesium carbonate (Scheme 32) [72]. The strategy can be extended to the synthesis of the cyclic selenium analogs 71 by utilizing elemental selenium and

Synthesis and stability of strongly acidic benzamide derivatives

• Frederik Diness,
• Niels J. Bjerrum and
• Mikael Begtrup

Beilstein J. Org. Chem. 2018, 14, 523–530, doi:10.3762/bjoc.14.38

• , 137.6, 132.23, 131.9, 127.6, 121.02 (q, J = 319.3 Hz); 19F NMR (470 MHz, MeOD) δ −80.60 (s); HRMS (TOF) m/z: [M − H]− calcd for C9H479BrF6N2O4S2−, 460.8706; found. 460.8766. 4-(1H-Benzo[d]imidazol-1-yl)-N-((trifluoromethyl)sulfonyl)benzamide (13): Cesium carbonate (163 mg, 5 equiv) was added to a glass

• closed screw cap vial to 100 °C for 1 min (color changed from yellow to deep red). A part of the catalyst mixture (0.2 mL) was added to a microwave glass vial containing a degassed mixture of 9d (33.1 mg, 0.1 mmol), 4-methoxyphenylboronic acid (22.8 mg, 0.15 mmol, 1.5 equiv) and cesium carbonate (100 mg

Synthesis of 2-aminosuberic acid derivatives as components of some histone deacetylase inhibiting cyclic tetrapeptides

• Shital Kumar Chattopadhyay,
• Suman Sil and
• Jyoti Prasad Mukherjee

Beilstein J. Org. Chem. 2017, 13, 2153–2156, doi:10.3762/bjoc.13.214

• an overall yield of 42% over five steps. One-pot deprotection–oxidation [14] of the oxazolidine moiety in 9 proceeded uneventfully to provide N-Boc-2-amino-6-heptenoic acid (10) in good yield. The latter was smothly protected as its methyl ester using methyl iodide in the presence of cesium carbonate

Syntheses of 3,4- and 1,4-dihydroquinazolines from 2-aminobenzylamine

• Jimena E. Díaz,
• Silvia Ranieri,
• Nadia Gruber and
• Liliana R. Orelli

Beilstein J. Org. Chem. 2017, 13, 1470–1477, doi:10.3762/bjoc.13.145

• required functionalization of both amino groups present in 2-ABA was achieved by different routes involving selective N-acylation and cesium carbonate-mediated N-alkylation reactions, avoiding protection/deprotection steps. The heterocycles were efficiently synthesized in short reaction times by microwave

• , necessary for the synthesis of dihydroquinazolines 2, were prepared by N-alkylation of the arylamino group present in compounds 4 using alkyl halides. In a previous work [63], we developed a methodology for the selective N-alkylation of anilines with ω-halonitriles in the presence of cesium carbonate and