Asymmetric synthesis of β-amino cyanoesters with contiguous tetrasubstituted carbon centers by halogen-bonding catalysis with chiral halonium salt

• Yasushi Yoshida,
• Maho Aono,
• Takashi Mino and
• Masami Sakamoto

Beilstein J. Org. Chem. 2025, 21, 547–555, doi:10.3762/bjoc.21.43

• tetrasubstituted carbon stereogenic centers [42][43][44][45][46]. In 2011, Shibasaki, Matsunaga and co-workers reported strontium or magnesium-catalyzed stereodivergent asymmetric Mannich reactions of an α-isothiocyanato ester with ketimines, which provided the products in excellent yields and

Deep-blue emitting 9,10-bis(perfluorobenzyl)anthracene

• Long K. San,
• Sebastian Balser,
• Brian J. Reeves,
• Tyler T. Clikeman,
• Yu-Sheng Chen,
• Steven H. Strauss and
• Olga V. Boltalina

Beilstein J. Org. Chem. 2025, 21, 515–525, doi:10.3762/bjoc.21.39

• (trifluoromethyl)benzene (1,4-C6H4(CF3)2, Central Glass Co., 99%); dimethyl sulfoxide (DMSO, Fisher Scientific, ACS grade); anhydrous magnesium sulfate (MgSO4, Fisher Scientific); Cu powder (Strem Chemicals, 99%); dichloromethane (EMD Chemicals, ACS grade); acetone (technical grade); THF (Aldrich/Merck, ACS grade

Synthesis of electrophile-tethered preQ₁ analogs for covalent attachment to preQ₁ RNA

• Laurin Flemmich and
• Ronald Micura

Beilstein J. Org. Chem. 2025, 21, 483–489, doi:10.3762/bjoc.21.35

• methanol (1.3 mL). Anhydrous magnesium sulfate (340 mg, 2.82 mmol, 10 equiv) and the respective amino alcohol (2.82 mmol, 10 equiv) were added. The mixture was sonicated for 30 minutes and subsequently stirred at room temperature for 16 h. After cooling to 0 °C, sodium borohydride (96.1 mg, 2.54 mmol, 9

Red light excitation: illuminating photocatalysis in a new spectrum

• Lucas Fortier,
• Corentin Lefebvre and
• Norbert Hoffmann

Beilstein J. Org. Chem. 2025, 21, 296–326, doi:10.3762/bjoc.21.22

• four compared to batch processes using conventional solvents. Recent advances have demonstrated that naturally derived photocatalysts, such as chlorophyll, a magnesium-based chlorin complex, can also efficiently drive photocatalytic transformations. In the study by Ouyang et al. chlorophyll extracted

Advances in the use of metal-free tetrapyrrolic macrocycles as catalysts

• Mandeep K. Chahal

Beilstein J. Org. Chem. 2024, 20, 3085–3112, doi:10.3762/bjoc.20.257

• functional versatility [44], and many of these resulting metal complexes are catalytically active [45][46][47]. These synthetic metalloporphyrins take inspiration from biological systems, such as hemes (iron complexes), chlorophylls (magnesium complexes), and vitamin B12 (cobalt complex). Contrary to

Synthesis of tricarbonylated propargylamine and conversion to 2,5-disubstituted oxazole-4-carboxylates

• Kento Iwai,
• Akari Hikasa,
• Kotaro Yoshioka,
• Shinki Tani,
• Kazuto Umezu and
• Nagatoshi Nishiwaki

Beilstein J. Org. Chem. 2024, 20, 2827–2833, doi:10.3762/bjoc.20.238

• , the molecular sieves were filtered off, and the filtrate was washed with water (50 mL × 2). The organic layer was dried over magnesium sulfate and concentrated under reduced pressure to afford diethyl α-acetoxy-α-(4-methylbenzoylamino)malonate (1a, 2.86 g, 8.1 mmol, 81% yield) as white solid. When

A review of recent advances in electrochemical and photoelectrochemical late-stage functionalization classified by anodic oxidation, cathodic reduction, and paired electrolysis

• Nian Li,
• Ruzal Sitdikov,
• Ajit Prabhakar Kale,
• Joost Steverlynck,
• Bo Li and
• Magnus Rueping

Beilstein J. Org. Chem. 2024, 20, 2500–2566, doi:10.3762/bjoc.20.214

Facile preparation of fluorine-containing 2,3-epoxypropanoates and their epoxy ring-opening reactions with various nucleophiles

• Yutaro Miyashita,
• Sae Someya,
• Tomoko Kawasaki-Takasuka,
• Tomohiro Agou and
• Takashi Yamazaki

Beilstein J. Org. Chem. 2024, 20, 2421–2433, doi:10.3762/bjoc.20.206

• executed at −78 °C under the action of LDA [29]. Moreover, by using the epoxyester 2b as the representative substrate, clarification of its reactivity was carried out by mixing with 1) heteronucleophiles like amines, thiols, and magnesium halides, 2) softer carbon nucleophiles such as malonates, and 3

Efficient one-step synthesis of diarylacetic acids by electrochemical direct carboxylation of diarylmethanol compounds in DMSO

• Hisanori Senboku and
• Mizuki Hayama

Beilstein J. Org. Chem. 2024, 20, 2392–2400, doi:10.3762/bjoc.20.203

• competitively occurs at the cathode, and an excess amount of electricity should therefore be necessary to obtain acceptable results. At the anode, on the other hand, dissolution of magnesium ions by electrochemical oxidation of magnesium metal occurs, preventing electrochemical oxidation of the product and

• intermediates at the anode. The produced acetate ion D and a magnesium ion form the salt E, which upon acid treatment during workup gives a diphenylacetic acid 2. The effects of DMSO as solvent are not clear at present, and one reasonable and acceptable aspect might be the solubility of the salt of intermediate

• cation of intermediate B is thought to be the magnesium ion, and the magnesium salt of B must be dissolved in the solvent. Although other magnesium salts, such as magnesium carbonate and magnesium oxalate, are also generated during the electrolysis, the magnesium salt of B would be dissolved sufficiently

Cell-free protein synthesis with technical additives – expanding the parameter space of in vitro gene expression

• Tabea Bartsch,
• Stephan Lütz and
• Katrin Rosenthal

Beilstein J. Org. Chem. 2024, 20, 2242–2253, doi:10.3762/bjoc.20.192

• the magnesium and potassium glutamate concentration, is 140 mM, which is less than half the concentration reported for the cellular environment. The cytoplasmic osmolarity of about 600 mOsm [16] is 50% higher than that calculated for CFPS. Taking into account all defined components, the water content

• for the calculation of the macromolecular concentration of the CFPS mix. Magnesium and potassium glutamate were considered as the contributing inorganic ions for the reference composition, for the DES corresponding salts were added to the value of 140 mM. For the osmolarity the concentrations of all

• defined components were multiplied with their number of dissociated particles, which was assumed as 1 for most components and 2 for magnesium and potassium glutamate and combined with the calculated concentration of macromolecules. For the water content, the amount of all known components was subtracted

Electrochemical allylations in a deep eutectic solvent

• Sophia Taylor and
• Scott T. Handy

Beilstein J. Org. Chem. 2024, 20, 2217–2224, doi:10.3762/bjoc.20.189

• (entry 1) resulted in good conversion to the allylation product, while zinc, magnesium, and graphite (Table 1, entries 3–5) displayed no reaction at all. This observation was somewhat surprising considering that both zinc and tin are very commonly used in conventional allylations in addition to as

• funnel with the aid of 10 mL of deionized (DI) water followed by 20 mL of diethyl ether. The organic layer was separated, dried with anhydrous magnesium sulfate, filtered, and the solvent removed in vacuo to afford the crude product, which was first analyzed by 1H NMR spectroscopy and then purified using

• potential conditions of 2 V with no reference electrode until 2.5 F/mol was passed. Following completion of each reaction, the mixture was transferred to a separatory funnel with the aid of 10 mL of DI water followed by 20 mL of diethyl ether. The organic layer was separated, dried with anhydrous magnesium

Multicomponent syntheses of pyrazoles via (3 + 2)-cyclocondensation and (3 + 2)-cycloaddition key steps

• Ignaz Betcke,
• Alissa C. Götzinger,
• Maryna M. Kornet and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2024, 20, 2024–2077, doi:10.3762/bjoc.20.178

• [135]. Following this, a one-pot process involving Michael addition/cyclocondensation with hydrazine derivatives leads to the corresponding pyrazoles. Since magnesium ions are formed during the Kumada coupling, the additive phenanthroline must be added during the cyclization step to prevent the

• coordination of the magnesium ions and subsequent hydrazine inactivation. The diversity-oriented nature of this consecutive four-component synthesis was used to synthesize 17 different donor/acceptor-substituted pyrazoles 108 in moderate to good yields (Scheme 39) [136]. The synthesis of bispyrazoles was also

1,2-Difluoroethylene (HFO-1132): synthesis and chemistry

• Liubov V. Sokolenko,
• Taras M. Sokolenko and
• Yurii L. Yagupolskii

Beilstein J. Org. Chem. 2024, 20, 1955–1966, doi:10.3762/bjoc.20.171

• magnesium [50][51] to form the desired 1,2-difluoroethylene as a mixture of E- and Z-isomers, which were separated by fractional distillation (boiling point: −53.1 °C for (E)-HFO-1132 and −26.0 °C for (Z)-HFO-1132 [47]). In patent literature, a variety of synthetic routes to HFO-1132 starting from other

Synthetic applications of the Cannizzaro reaction

• Bhaskar Chatterjee,
• Dhananjoy Mondal and
• Smritilekha Bera

Beilstein J. Org. Chem. 2024, 20, 1376–1395, doi:10.3762/bjoc.20.120

• proceeded with modest to good yields, in the range of 40–82%, and depicts the Cannizzaro reaction in the transfer hydrogenation process [35]. A facile room temperature Cannizzaro reaction protocol was established by Abaee et al. employing magnesium bromide etherate and triethylamine in dichloromethane [77

Enhancing structural diversity of terpenoids by multisubstrate terpene synthases

• Min Li and
• Hui Tao

Beilstein J. Org. Chem. 2024, 20, 959–972, doi:10.3762/bjoc.20.86

• , that bind trinuclear magnesium clusters for diphosphate abstraction, whereas class II TSs have a DXDD motif that acts as the catalytic acid. Recently, several novel unconventional TSs that share low sequence and structural similarities with classical TSs have been discovered and comprehensively

Synthesis and biological profile of 2,3-dihydro[1,3]thiazolo[4,5-b]pyridines, a novel class of acyl-ACP thioesterase inhibitors

• Jens Frackenpohl,
• David M. Barber,
• Guido Bojack,
• Birgit Bollenbach-Wahl,
• Ralf Braun,
• Rahel Getachew,
• Sabine Hohmann,
• Kwang-Yoon Ko,
• Karoline Kurowski,
• Bernd Laber,
• Rebecca L. Mattison,
• Thomas Müller,
• Anna M. Reingruber,
• Dirk Schmutzler and
• Andrea Svejda

Beilstein J. Org. Chem. 2024, 20, 540–551, doi:10.3762/bjoc.20.46

• was added, followed by thorough extraction. The combined organic layer was dried over magnesium sulfate, filtered, and dried under reduced pressure. The remaining residue was purified via column chromatography (gradient ethyl acetate/hexane) to afford 6-bromo-5-(2-fluorophenyl)[1,3]thiazolo[4,5-b

• pyrrolidinedithiocarbamate (328 mg, 2.00 mmol, 0.44 equiv). The reaction mixture was stirred for 1 h at room temperature, and the organic layer was washed with saturated sodium hydrogencarbonate solution, dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The remaining residue was purified via

(E,Z)-1,1,1,4,4,4-Hexafluorobut-2-enes: hydrofluoroolefins halogenation/dehydrohalogenation cascade to reach new fluorinated allene

• Nataliia V. Kirij,
• Andrey A. Filatov,
• Yurii L. Yagupolskii,
• Sheng Peng and
• Lee Sprague

Beilstein J. Org. Chem. 2024, 20, 452–459, doi:10.3762/bjoc.20.40

• the corresponding =CF2 containing products [10]. In addition to complexes of aluminum and boron, several magnesium and lithium silyl reagents were prepared and proved to be good nucleophiles in reactions with (Z)-1,1,1,4,4,4-hexafluorobut-2-ene, as a result of which the corresponding

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

• -halides [115]. Their optimized reaction conditions required a NiII precursor, 2,2’-bipyridine (bpy) as ligand, silver nitrate (AgNO3) as an additive and the combination of a magnesium (Mg) sacrificial anode and a RVC cathode (Scheme 35A). A crucial discovery in advancing this methodology was the in situ

A deep-red fluorophore based on naphthothiadiazole as emitter with hybridized local and charge transfer and ambipolar transporting properties for electroluminescent devices

• Suangsiri Arunlimsawat,
• Patteera Funchien,
• Pongsakorn Chasing,
• Atthapon Saenubol,
• Taweesak Sudyoadsuk and
• Vinich Promarak

Beilstein J. Org. Chem. 2023, 19, 1664–1676, doi:10.3762/bjoc.19.122

• increasing voltage (CELIV) or MIS-CELIV technique [59][60][61]. Electron- and hole-only MIS devices were fabricated with the structures of indium tin oxide (ITO)/magnesium fluoride (MgF2) (20 nm)/TPECNz (100 nm)/lithium fluoride (LiF) (1 nm)/aluminum (Al) (100 nm) and ITO/MgF2 (20 nm)/TPECNz (100 nm

Tying a knot between crown ethers and porphyrins

• Maksym Matviyishyn and
• Bartosz Szyszko

Beilstein J. Org. Chem. 2023, 19, 1630–1650, doi:10.3762/bjoc.19.120

• sodium(I), zinc(II), magnesium(II), and barium(II) [106][107][108][109]. Association constants of the reported host–guest complexes showed similar values to those of diazacrown ethers [110][111]. Johnston and Gunter presented a crown ether-capped porphyrin receptor 10, which showed unexpected binding

Visible-light-induced nickel-catalyzed α-hydroxytrifluoroethylation of alkyl carboxylic acids: Access to trifluoromethyl alkyl acyloins

• Feng Chen,
• Xiu-Hua Xu,
• Zeng-Hao Chen,
• Yue Chen and
• Feng-Ling Qing

Beilstein J. Org. Chem. 2023, 19, 1372–1378, doi:10.3762/bjoc.19.98

• the synthesis of trifluoromethyl aromatic acyloins. Maekawa’s group [24] developed a tandem reaction of the reductive coupling between arylaldehydes and ethyl trifluoroacetate in the presence of magnesium and chlorotrimethylsilane, followed by desilylation to produce the trifluoromethyl aromatic

Synthesis of ether lipids: natural compounds and analogues

• Marco Antônio G. B. Gomes,
• Alicia Bauduin,
• Chloé Le Roux,
• Romain Fouinneteau,
• Wilfried Berthe,
• Mathieu Berchel,
• Hélène Couthon and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2023, 19, 1299–1369, doi:10.3762/bjoc.19.96

First synthesis of acylated nitrocyclopropanes

• Kento Iwai,
• Rikiya Kamidate,
• Khimiya Wada,
• Haruyasu Asahara and
• Nagatoshi Nishiwaki

Beilstein J. Org. Chem. 2023, 19, 892–900, doi:10.3762/bjoc.19.67

• , 80 mmol), the mixture was extracted with ethyl acetate (30 mL × 3), and the organic layer was washed with brine (30 mL × 1), dried over magnesium sulfate, and concentrated to afford nitrostyrene 2a (17.4 g, 71%, mp 56–58 °C) as a yellow solid. Nitrostyrene 2b (mp 112–114 °C) was prepared in the same

Asymmetric tandem conjugate addition and reaction with carbocations on acylimidazole Michael acceptors

• Brigita Mudráková,
• Renata Marcia de Figueiredo,
• Jean-Marc Campagne and
• Radovan Šebesta

Beilstein J. Org. Chem. 2023, 19, 881–888, doi:10.3762/bjoc.19.65

• , imines, other Michael acceptors, or alkyl halides. Our group is developing trapping of metal enolates with stabilized carbocations and could show that magnesium enolates generated from enones [22], unsaturated amides [23], or heterocycles reacted with tropylium, dithiolylium or flavylium cations [24

Eschenmoser coupling reactions starting from primary thioamides. When do they work and when not?

• Lukáš Marek,
• Jiří Váňa,
• Jan Svoboda and
• Jiří Hanusek

Beilstein J. Org. Chem. 2023, 19, 808–819, doi:10.3762/bjoc.19.61

• ). α-Bromophenylacetic acid amides (4a,b) were prepared from 2-bromo-2-phenylacetyl chloride [38] and the corresponding amine in DCM or toluene at reduced temperature (see Supporting Information File 1). Thiobenzamides and thiobenzanilides were prepared by magnesium chloride-catalyzed thiolysis of