Fritsch–Buttenberg–Wiechell rearrangement of magnesium alkylidene carbenoids leading to the formation of alkynes

• Tsutomu Kimura,
• Koto Sekiguchi,
• Akane Ando and
• Aki Imafuji

Beilstein J. Org. Chem. 2021, 17, 1352–1359, doi:10.3762/bjoc.17.94

• treated with organometallic reagents to evaluate which combination of sulfoxides and organometallic reagents yielded alkynes the most efficiently. The use of 1-chlorovinyl p-tolyl sulfoxide and isopropylmagnesium chloride was optimal for this purpose. A variety of 1-chlorovinyl p-tolyl sulfoxides were

• prepared from carbonyl compounds and chloromethyl p-tolyl sulfoxide and were converted into alkynes via the sulfoxide/magnesium exchange reaction and subsequent Fritsch–Buttenberg–Wiechell (FBW) rearrangement of the resulting magnesium alkylidene carbenoids. The mechanism of the FBW rearrangement of

• magnesium alkylidene carbenoids was studied by using 13C-labeled sulfoxides and by using DFT calculations. Keywords: alkyne; 1-chlorovinyl p-tolyl sulfoxide; DFT calculation; Fritsch–Buttenberg–Wiechell rearrangement; magnesium alkylidene carbenoid; Introduction Alkynes are important compounds in organic

A comprehensive review of flow chemistry techniques tailored to the flavours and fragrances industries

• Guido Gambacorta,
• James S. Sharley and
• Ian R. Baxendale

Beilstein J. Org. Chem. 2021, 17, 1181–1312, doi:10.3762/bjoc.17.90

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

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

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

• using alkali salt promoters (Na2CO3, NaHCO3, Na2SO4 or K2SO4, Figure 4). PET wastes, including highly coloured and multilayered PET, could be used as substrate. More recently, it was demonstrated that the addition of a cosolvent for PET, such as dimethyl sulfoxide (DMSO), NMP, nitrobenzene or aniline to

CF₃-substituted carbocations: underexploited intermediates with great potential in modern synthetic chemistry

• Anthony J. Fernandes,
• Armen Panossian,
• Bastien Michelet,
• Agnès Martin-Mingot,
• Frédéric R. Leroux and
• Sébastien Thibaudeau

Beilstein J. Org. Chem. 2021, 17, 343–378, doi:10.3762/bjoc.17.32

• of 93%, the Pummerer rearrangement of sulfoxide 214 under harsh conditions turned out to be less efficient, affording 204f in only 42% yield. This reaction is thought to proceed stepwise via a first oxidative electron transfer, followed by deprotonation, a second oxidative electron transfer, and

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

• Å, respectively. Every ureido group held one molecule of DMSO via synchronous hydrogen bonding interactions between the two NH protons and a sulfoxide oxygen atom (Figure 3a). The S=O···H–N distances were 1.995, 2.285, 2.033, and 2.328 Å, indicating strong interactions in the solid state. At the

Selective recognition of ATP by multivalent nano-assemblies of bisimidazolium amphiphiles through “turn-on” fluorescence response

• Rakesh Biswas,
• Surya Ghosh,
• Shubhra Kanti Bhaumik and
• Supratim Banerjee

Beilstein J. Org. Chem. 2020, 16, 2728–2738, doi:10.3762/bjoc.16.223

• ). Preparation of solutions A. Preparation of PBImN solutions Initially, stock solutions of PBImNs (N = 4, 10, 12, 14) were prepared by dissolving the solid powders in spectroscopic grade dimethyl sulfoxide (DMSO). These concentrated DMSO solutions were then diluted to 5 mM tris-HCl buffer in 10 mM NaCl made in

The B & B approach: Ball-milling conjugation of dextran with phenylboronic acid (PBA)-functionalized BODIPY

• Patrizia Andreozzi,
• Lorenza Tamberi,
• Elisamaria Tasca,
• Gina Elena Giacomazzo,
• Marta Martinez,
• Mirko Severi,
• Marco Marradi,
• Stefano Cicchi,
• Sergio Moya,
• Giacomo Biagiotti and
• Barbara Richichi

Beilstein J. Org. Chem. 2020, 16, 2272–2281, doi:10.3762/bjoc.16.188

• roughly equimolar amount of Dex and 1, in a glucose units/1 molar ratio of 60:1 (assuming an average molecular weight for Dex of 10 kDa). For the labeling in solution, Dex was dissolved in dry dimethyl sulfoxide (DMSO) and PBA-BODIPY (1) was added in roughly equimolar amounts (Scheme 1, route A). The

• 0.044 mmol), 17 mg of PBA-BODIPY (1, 0.044 mmol), and 6.6 mL of dry dimethyl sulfoxide. The mixture was stirred for 6 h, then the product was precipitated in cold ethanol (50 mL), and filtered over a 0.2 µm nylon membrane. The powder was recovered and dispersed (6.8 mg/mL) in ethanol and sonicated for 5

One-pot and metal-free synthesis of 3-arylated-4-nitrophenols via polyfunctionalized cyclohexanones from β-nitrostyrenes

• Haruyasu Asahara,
• Minami Hiraishi and
• Nagatoshi Nishiwaki

Beilstein J. Org. Chem. 2020, 16, 1830–1836, doi:10.3762/bjoc.16.150

• -nitrocyclohexanones. When the reaction was conducted in the presence of water, the cyclohexenes were efficiently hydrolyzed into cyclohexanones. Subsequent aromatization by heating the cyclohexanone with a catalytic amount of iodine in dimethyl sulfoxide gave 3-arylated-4-nitrophenols. The reaction of nitrostyrenes

• using iodine was then attempted (Table 2). The reaction did not proceed in toluene or acetonitrile (Table 2, entries 1 and 2), but dimethyl sulfoxide (DMSO) was effective for the aromatization, and nitrophenol 5a was obtained in 26% yield (Table 2, entry 3) [21][22][23]. This reaction proceeded

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

• -oxide (TMANO), and dimethyl sulfoxide (DMSO). Once a new coordination vacancy has been opened on one of the cobalt centers, coordination of the olefin sets the stage for the subsequent C–C bond forming steps. The olefin is inserted into the less hindered Co–C bond, determining both the regio- and

Mechanochemical green synthesis of hyper-crosslinked cyclodextrin polymers

• Alberto Rubin Pedrazzo,
• Fabrizio Caldera,
• Marco Zanetti,
• Silvia Lucia Appleton,
• Nilesh Kumar Dhakar and
• Francesco Trotta

Beilstein J. Org. Chem. 2020, 16, 1554–1563, doi:10.3762/bjoc.16.127

• aprotic liquids (e.g., N,N-dimethylformamide or dimethyl sulfoxide), which affect the final result, especially for potential biomedical applications. This article describes a new, green synthetic pathway through mechanochemistry, in particular via ball milling and using 1,1-carbonyldiimidazole as the

• catalyst, if necessary. The solvents of choice were usually organic polar aprotic liquids, for example, N,N-dimethylformamide or dimethyl sulfoxide (DMSO). An alternative synthetic route relied on interfacial polymerization, where two immiscible solutions, one consisting of CDs dissolved in an alkaline

• . The solubility in various common solvents (water, acetone, ethanol, N,N-dimethylformamide or dimethyl sulfoxide, diethyl ether, and petroleum ether) of the new nanosponges was tested. Like nanosponges obtained from batch experiments, also the ones from ball-mill synthesis, as expected, were insoluble

Development of fluorinated benzils and bisbenzils as room-temperature phosphorescent molecules

• Shigeyuki Yamada,
• Takuya Higashida,
• Yizhou Wang,
• Masato Morita,
• Takuya Hosokai,
• Kaveendra Maduwantha,
• Kaveenga Rasika Koswattage and
• Tsutomu Konno

Beilstein J. Org. Chem. 2020, 16, 1154–1162, doi:10.3762/bjoc.16.102

• phosphorescent molecules. These compounds were separately converted from the corresponding fluorinated bistolanes via PdCl2-catalyzed oxidation by dimethyl sulfoxide, while nonfluorinated bistolane provided the corresponding bisbenzil derivatives exclusively in a similar manner. Intensive investigations of the

• derivatives. The PdCl2-catalyzed oxidation of the C≡C bonds in 1 by dimethyl sulfoxide (DMSO) was performed according to a previously reported procedure (Scheme 1) [33][34]. The methoxy-substituted fluorinated bistolane 1a was prepared from commercially available 4-ethynylanisole in four facile steps

• pathway for fluorinated benzil (2) and bisbenzil (3) derivatives. Proposed mechanism of Pd(II)-catalyzed alkyne oxidation by dimethyl sulfoxide (DMSO). Photophysical data from ultraviolet (UV)-visible absorption and steady-state photoluminescence (PL) measurementsa. Supporting Information Experimental

Synthesis of novel multifunctional carbazole-based molecules and their thermal, electrochemical and optical properties

• Nuray Altinolcek,
• Ahmet Battal,
• Mustafa Tavasli,
• William J. Peveler,
• Holly A. Yu and
• Peter J. Skabara

Beilstein J. Org. Chem. 2020, 16, 1066–1074, doi:10.3762/bjoc.16.93

• microscopic solvent polarity [43][44], ET(30), increased from toluene to dimethyl sulfoxide (see also Table 3). A 141 nm red-shift was observed for 7a (from 465 nm to 606 nm) and an 86 nm red-shift was observed for 7b (from 423 nm to 509 nm). In comparison for 7b, this red-shift was more pronounced for 7a

Accelerating fragment-based library generation by coupling high-performance photoreactors with benchtop analysis

• Quentin Lefebvre,
• Christophe Salomé and
• Thomas C. Fessard

Beilstein J. Org. Chem. 2020, 16, 982–988, doi:10.3762/bjoc.16.87

• were slightly altered: a smaller excess of amine was used, and dimethyl sulfoxide (DMSO) was chosen as solvent instead of dimethylformamide (DMF) or dimethylacetamide (DMA) to improve work-up and purification. The workflow was devised to ensure maximal productivity, using parallel experimentation

Recent applications of porphyrins as photocatalysts in organic synthesis: batch and continuous flow approaches

• Rodrigo Costa e Silva,
• Luely Oliveira da Silva,
• Aloisio de Andrade Bartolomeu,
• Timothy John Brocksom and
• Kleber Thiago de Oliveira

Beilstein J. Org. Chem. 2020, 16, 917–955, doi:10.3762/bjoc.16.83

• medicine and pharmacology [94], justifying many studies on this topic. The accepted mechanism for sulfide oxidation to sulfoxide involves the chemical quenching of singlet oxygen by sulfur compounds which leads to the persulfoxide intermediate. From this intermediate, a variety of reaction pathways are

• of A) thioanisole to methyl phenyl sulfoxide and B) various aryl sulfides, using 2D-PdPor-COF, 3D-PdPor-COF, and p-PdPor-CHO. General mechanism for oxidation of amines to imines. Oxidation of secondary amines to imines. Oxidation of secondary amines using Pd-TPFPP as photocatalyst. Oxidative amine

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

• either CuCl/quinoxP* or their in-house-developed chiral sulfoxide phosphine ligand (SOP). Excellent diastereo- and enantioselectivities were obtained. A gram scale synthesis of (S)-naproxen was also described as a “real world” application [106]. From previous findings involving trapping of a vinylarene

Architecture and synthesis of P,N-heterocyclic phosphine ligands

• Wisdom A. Munzeiwa,
• Bernard Omondi and
• Vincent O. Nyamori

Beilstein J. Org. Chem. 2020, 16, 362–383, doi:10.3762/bjoc.16.35

• the red phosphorus with 2-bromopyridine in potassium hydroxide/dimethyl sulfoxide emulsion, pyridylphosphine was obtained in moderate yields. Traces of phosphine oxide were present as evidenced by the observation of two phosphorus peaks in the 15P NMR spectrum. An optimized method via Grignard

Light-controllable dithienylethene-modified cyclic peptides: photoswitching the in vivo toxicity in zebrafish embryos

• Sergii Afonin,
• Oleg Babii,
• Aline Reuter,
• Volker Middel,
• Masanari Takamiya,
• Uwe Strähle,
• Igor V. Komarov and
• Anne S. Ulrich

Beilstein J. Org. Chem. 2020, 16, 39–49, doi:10.3762/bjoc.16.6

• corresponding peptide dissolved in dimethyl sulfoxide (final dimethyl sulfoxide concentration was 0.2%). Double-concentrated peptide stock solutions (64–512 µg/mL) were prepared by weighing lyophilized peptides, dissolving in 10% dimethyl sulfoxide and constructing two-fold dilution series with ten–eleven

Diversity-oriented synthesis of spirothiazolidinediones and their biological evaluation

• Sambasivarao Kotha,
• Gaddamedi Sreevani,
• Lilya U. Dzhemileva,
• Milyausha M. Yunusbaeva,
• Usein M. Dzhemilev and
• Vladimir A. D’yakonov

Beilstein J. Org. Chem. 2019, 15, 2774–2781, doi:10.3762/bjoc.15.269

• incubator. The cells were then incubated with the test compounds at different concentrations for an additional 24 h. Control wells were prepared by the addition of dimethyl sulfoxide (DMSO, 1%). At the end of this incubation, 20 μL of MTT (5 mg/mL in PBS) was added to each well. After incubation for 4 h

A review of asymmetric synthetic organic electrochemistry and electrocatalysis: concepts, applications, recent developments and future directions

• Munmun Ghosh,
• Valmik S. Shinde and
• Magnus Rueping

Beilstein J. Org. Chem. 2019, 15, 2710–2746, doi:10.3762/bjoc.15.264

• of 38 to the corresponding sulfoxide 39 with excellent chemical yield although the value of enantiomeric excess was considerably low (Scheme 16) [46]. A few years later, Komori and Nonaka, in two consecutive reports, established a modified method for the asymmetric electrochemical oxidation of alkyl

Arylisoquinoline-derived organoboron dyes with a triaryl skeleton show dual fluorescence

• Vânia F. Pais,
• Tristan Neumann,
• Ignacio Vayá,
• M. Consuelo Jiménez,
• Abel Ros and
• Uwe Pischel

Beilstein J. Org. Chem. 2019, 15, 2612–2622, doi:10.3762/bjoc.15.254

• (dichloromethane, acetonitrile, dimethyl sulfoxide), are summarized in Table 1. A first inspection of these data showed that the UV–vis absorption spectra feature the typical bands corresponding to their aromatic moieties (see Figure 2 for the spectra in acetonitrile). For example, for the dyes 18 and 19 π–π

• moiety [37][38], while the donor is related to the electronically variable aryl residue. Comparing the emission maxima of the dyes in the less polar dichloromethane with those in the highly polar dimethyl sulfoxide, additional trends can be seen. Thus, dye 17 shows only a slight bathochromic shift of the

• two stereogenic axes. The dyes show pronounced dual emission patterns with long-wavelength maxima close to 600 nm in polar solvents such as acetonitrile or dimethyl sulfoxide. The emission maxima of the long-wavelength band vary systematically with the electron-donor strength of the additional aryl

Probing of local polarity in poly(methyl methacrylate) with the charge transfer transition in Nile red

• Aydan Yadigarli,
• Qimeng Song,
• Sergey I. Druzhinin and
• Holger Schönherr

Beilstein J. Org. Chem. 2019, 15, 2552–2562, doi:10.3762/bjoc.15.248

• ][66] might be caused by remaining traces of solvent from PMMA solution (toluene) [66] in close vicinity to NR molecules, similar to results for NR in poly(vinylidene fluoride) films cast from dimethyl sulfoxide [15]. This notion is supported by fluorescence maxima (λf) of NR in PMMA at the excitation

In water multicomponent synthesis of low-molecular-mass 4,7-dihydrotetrazolo[1,5-a]pyrimidines

• Irina G. Tkachenko,
• Sergey A. Komykhov,
• Vladimir I. Musatov,
• Svitlana V. Shishkina,
• Viktoriya V. Dyakonenko,
• Vladimir N. Shvets,
• Mikhail V. Diachkov,
• Valentyn A. Chebanov and
• Sergey M. Desenko

Beilstein J. Org. Chem. 2019, 15, 2390–2397, doi:10.3762/bjoc.15.231

• sulfoxide solutions. Ascorbic acid served as positive control. Among the tested compounds 9f showed the best results at 10−3 mol/L concentration and compound 9d exhibited the highest AOA at the other tested concentrations. The results of the radical scavenging experiments are collected in Table 1 and are

• of 0.1 mmol/L DPPH (2 mL) in methanol was added to 2 mL of a solution of the investigated substance (9, 11, 14) in dimethyl sulfoxide (DMSO) at different concentrations (10−3, 10−5, 10−7 mol/L). The control solution was prepared by mixing 2 mL of DMSO and 0.1 mmol/L DPPH solution (2 mL). The mixture

Attempted synthesis of a meta-metalated calix[4]arene

• Christopher D. Jurisch and
• Gareth E. Arnott

Beilstein J. Org. Chem. 2019, 15, 1996–2002, doi:10.3762/bjoc.15.195

• this using a pyridyl sulfoxide directing group and palladium as the metal, but in this case the palladium caused a double C–H activation and formed an impressive bridge to the adjacent calix[4]arene aromatic ring [14]. The question for us was whether this bridge formation was a general principle or