Salen–scandium(III) complex-catalyzed asymmetric (3 + 2) annulation of aziridines and aldehydes

• Linqiang Wang and
• Jiaxi Xu

Beilstein J. Org. Chem. 2025, 21, 1087–1094, doi:10.3762/bjoc.21.86

• was refluxed over sodium with benzophenone as an indicator and freshly distilled prior to use. Column chromatography was performed on silica gel (normal phase, 200–300 mesh) from Anhui Liangchen Silicon Material Co., Ltd. or basic aluminum oxide (pH 9–10) from Shanghai Titan Technology Co., Ltd

• . Petroleum ether (PE, 60–90 °C fraction) and ethyl acetate (EA) were used as eluent. Reactions were monitored by thin-layer chromatography (TLC) on GF254 silica gel plates (0.2 mm) from Anhui Liangchen Silicon Material Co., Ltd. The plates were visualized by UV light. 1H NMR (400 MHz) and 13C NMR (101 MHz

Recent advances in controllable/divergent synthesis

• Jilei Cao,
• Leiyang Bai and
• Xuefeng Jiang

Beilstein J. Org. Chem. 2025, 21, 890–914, doi:10.3762/bjoc.21.73

• imides and TMS-alkynes, enabling the rapid construction of S(VI)–C(sp2) or S(VI)–C(sp) bonds efficiently (Scheme 24) [55]. This linkage utilizes the high bond dissociation energy (BDE = 135 kcal/mol) of silicon–fluorine bonds, employing trifluoroborate as a fluorine transfer reagent to simultaneously

• cleave the S(VI)–F bond and activate the Si–C bond. DFT calculations indicate that the reaction proceeds via the formation of a difluoroborate phenylacetylene intermediate 94’’ by in situ generation from boron trifluoride etherate and silicon-protected phenylacetylene 94, which activates the S–F bond of

Development and mechanistic studies of calcium–BINOL phosphate-catalyzed hydrocyanation of hydrazones

• Carola Tortora,
• Christian A. Fischer,
• Sascha Kohlbauer,
• Alexandru Zamfir,
• Gerd M. Ballmann,
• Jürgen Pahl,
• Sjoerd Harder and
• Svetlana B. Tsogoeva

Beilstein J. Org. Chem. 2025, 21, 755–765, doi:10.3762/bjoc.21.59

• the computational investigation, could not be isolated either – probably due to its high sensitivity to hydrolysis. However, a 2D 1H-15N NMR correlation spectrum showed no interactions of hydrogen nuclei in silicon-bound methyl groups and any of the nitrogens in the product. This led us to conclude

• that silicon is bound via the carbonyl oxygen in 12, as also shown by DFT computations. This is further corroborated by observation of a 13C NMR signal at 146 ppm for an sp2 carbon in the backbone of the product, which fits better for a C=N than a C=O bond. Recovery of the catalyst resting state 7 is

• achieved by reacting 11 with stoichiometric reagent TMSCN (8). This "reloads" calcium with cyanide and replaces TMS-bound isolated product 12 from the metal complex and in which silicon, rather than calcium, is bound to the carbonyl oxygen. The addition reaction itself is rather exothermic (Figure 3) 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

• ; perfluorobenzylation; photochemistry; Introduction The revolution of small organic molecules in the semiconductor industry continues to progress, replacing some silicon and metal-based electronic components. Acenes, such as anthracene (ANTH) and its higher homologues, represent some of the most studied materials that

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

• hemoglobin, and silicon by selectively irradiating a specific area of the reaction medium with red light (660 nm) or blue light (456 nm), respectively (Scheme 2). The authors have demonstrated that this polymerization reaction proceeded much more efficiently under red light irradiation. Indeed, red light can

• %. Beyond their coordination with transition metals, phthalocyanin ligands also exhibit remarkable photoreactivity in supporting non-metallic central elements. Recent work by Amara et al. highlights the efficiency of silicon-based phthalocyanin complexes in red-light-driven photooxidation processes, marking

• a shift away from the reliance on traditional heavy-metal catalysts [38]. By utilizing silicon as a cheap, non-toxic, and abundantly available element, silicon-based phthalocyanin complex derivatives represent a more sustainable alternative to precious metal-based photocatalysts such as ruthenium or

Advances in radical peroxidation with hydroperoxides

• Oleg V. Bityukov,
• Pavel Yu. Serdyuchenko,
• Andrey S. Kirillov,
• Gennady I. Nikishin,
• Vera A. Vil’ and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2024, 20, 2959–3006, doi:10.3762/bjoc.20.249

Asymmetric organocatalytic synthesis of chiral homoallylic amines

• Nikolay S. Kondratyev and
• Andrei V. Malkov

Beilstein J. Org. Chem. 2024, 20, 2349–2377, doi:10.3762/bjoc.20.201

• excellent yields (77–91%) and excellent enantioselectivities (90–96%) on a millimolar scale (Scheme 13). It is worth noting the use of optimised minimal excess of allyltributyltin (65), which to some extent addresses the higher toxicity of trialkylstannanes compared to their silicon counterparts. The

Discovery of antimicrobial peptides clostrisin and cellulosin from Clostridium: insights into their structures, co-localized biosynthetic gene clusters, and antibiotic activity

• Moisés Alejandro Alejo Hernandez,
• Katia Pamela Villavicencio Sánchez,
• Rosendo Sánchez Morales,
• Karla Georgina Hernández-Magro Gil,
• David Silverio Moreno-Gutiérrez,
• Eddie Guillermo Sanchez-Rueda,
• Yanet Teresa-Cruz,
• Brian Choi,
• Armando Hernández Garcia,
• Alba Romero-Rodríguez,
• Oscar Juárez,
• Siseth Martínez-Caballero,
• Mario Figueroa and
• Corina-Diana Ceapă

Beilstein J. Org. Chem. 2024, 20, 1800–1816, doi:10.3762/bjoc.20.159

• performed using a Digital Instruments NanoScope V, acquiring 1024 samples per line with silicon nitride cantilevers possessing a nominal spring constant of 0.32 Nm−1 and a 0.8–1.0 Hz scan rate. Imaging was conducted at room temperature using the ScanAsyst™ air mode. Images were processed using NanoScope

Generation of alkyl and acyl radicals by visible-light photoredox catalysis: direct activation of C–O bonds in organic transformations

• Mithu Roy,
• Bitan Sardar,
• Itu Mallick and
• Dipankar Srimani

Beilstein J. Org. Chem. 2024, 20, 1348–1375, doi:10.3762/bjoc.20.119

• conventional metal hydrides, such as tin or silicon hydrides. The reaction mechanism is interesting since first, a Lewis acid–base adduct is generated by interaction of Et3N with a boron atom of bis(catecholato)diboron (B2cat2, 19). As a result, one of the catecholate ligands experiences an increase in

Two-fold addition reaction of silylene to C₆₀: structural and electronic properties of a bis-adduct

• Masahiro Kako,
• Masato Kai,
• Masanori Yasui,
• Michio Yamada,
• Yutaka Maeda and
• Takeshi Akasaka

Beilstein J. Org. Chem. 2024, 20, 1179–1188, doi:10.3762/bjoc.20.100

• 305-8577, Japan 10.3762/bjoc.20.100 Abstract The addition reaction of C60 with silylene 1, a silicon analog of carbene, yielded the corresponding bis-adduct 3. The structure of 3 was determined by single-crystal X-ray structure analysis, representing the first example of a crystal structure of a

• silicon analog of carbene, were described as providing silirane (silacyclopropane)-type 6,6-mono-adducts Dip2SiC60 (2, Scheme 1) and Dip2SiC70 [15][16]. Furthermore, bis-adducts (Dip2Si)2C60 and (Dip2Si)2C70 were obtained as byproducts, but no details of these bis-adducts have been clarified [15][16]. The

• results demonstrated that the electronic properties of product 2 were altered considerably compared to that of pristine C60 mainly because silicon atoms are less electronegative. Electron-donating effects of silyl groups in fullerene derivatives were also rationalized in terms of σ–π conjugations between

Perspectives on push–pull chromophores derived from click-type [2 + 2] cycloaddition–retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes

• Michio Yamada

Beilstein J. Org. Chem. 2024, 20, 125–154, doi:10.3762/bjoc.20.13

Multi-redox indenofluorene chromophores incorporating dithiafulvene donor and ene/enediyne acceptor units

• Christina Schøttler,
• Kasper Lund-Rasmussen,
• Line Broløs,
• Philip Vinterberg,
• Ema Bazikova,
• Viktor B. R. Pedersen and
• Mogens Brøndsted Nielsen

Beilstein J. Org. Chem. 2024, 20, 59–73, doi:10.3762/bjoc.20.8

• compound is shown below, in which the hydrogen atoms are omitted for clarity. Atoms are colored grey (carbon), white (hydrogen), brown (bromine), pale-yellow (silicon). Labels of bonds within five-membered ring. Synthesis of IF-DTF ketones 9–12 and dimer 13. Further functionalization of the IF-DTF ketone

Preparing a liquid crystalline dispersion of carbon nanotubes with high aspect ratio

• Keiko Kojima,
• Nodoka Kosugi,
• Hirokuni Jintoku,
• Kazufumi Kobashi and
• Toshiya Okazaki

Beilstein J. Org. Chem. 2024, 20, 52–58, doi:10.3762/bjoc.20.7

• flowing air (200 mL/min) at a ramping rate of 1 °C/min. The Raman and absorption spectra were obtained from DWCNT thin film on a silicon substrate. The DWCNT thin film was prepared using vacuum filtration. Raman measurements were conducted using a HORIBA T64000 532 nm laser, while far-infrared (FIR

• ) analysis (CPS Instruments, CPS 24000UHR (CR-39)). The shape and size of the DWCNTs in dispersion were observed by settling them on a silicon substrate, washed with acetone, and exposed to UV light for 20 minutes using an ozone cleaner (Meiwafosis, PC-450 plus) via dip-coating. The structures of DWCNTs were

Radical chemistry in polymer science: an overview and recent advances

• Zixiao Wang,
• Feichen Cui,
• Yang Sui and
• Jiajun Yan

Beilstein J. Org. Chem. 2023, 19, 1580–1603, doi:10.3762/bjoc.19.116

• , and monomers [127][128][129]. Polysiloxanes are another class of crosslinkable polymers. Modern silicone industry typically uses Pt-catalyzed hydrosilylation to crosslink multi-vinyl polysiloxane with silicon hydride compounds to manufacture silicone rubbers [130]. However, hydrosilylation may also be

Application of N-heterocyclic carbene–Cu(I) complexes as catalysts in organic synthesis: a review

• Nosheen Beig,
• Varsha Goyal and
• Raj K. Bansal

Beilstein J. Org. Chem. 2023, 19, 1408–1442, doi:10.3762/bjoc.19.102

• employed as catalysts in a variety of organic reactions. In this section, a brief review on the use of NHC–Cu(I) complexes as catalysts in organic synthesis is presented. 2.1 Hydrosilylation reactions Hydrosilylation reactions involve the addition of a silicon–hydrogen (Si–H) moiety across a carbon–carbon

• or carbon–heteroatom double bond, resulting in the formation of a new carbon–silicon (C–Si) or heteroatom–Si (X–Si) bond (Scheme 34). This reaction is widely used in the synthesis of organosilicon compounds and in the modification of surfaces with silicon-containing molecules. NHC–Cu complexes have

Selective construction of dispiro[indoline-3,2'-quinoline-3',3''-indoline] and dispiro[indoline-3,2'-pyrrole-3',3''-indoline] via three-component reaction

• Ziying Xiao,
• Fengshun Xu,
• Jing Sun and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2023, 19, 1234–1242, doi:10.3762/bjoc.19.91

• solvent by rotatory evaporation at reduced pressure, the residue was subjected to column chromatography (silicon gel, 300–400 mesh) with petroleum ether and ethyl acetate (v/v = 1:1) to give the pure product for analysis. Ethyl rel-(3R,3'S,4'R)-1,1''-dibenzyl-5,5''-dichloro-7',7'-dimethyl-2,2'',5'-trioxo

• mixture was heated at 50 °C for seven hours. After removing the solvent by rotatory evaporation at reduced pressure, the residue was subjected to column chromatography (silicon gel, 300–400 mesh) with petroleum ether and ethyl acetate (v/v = 4:1) to give the pure product for analysis. rel-(3R,3'S,4'R)-1,1

Synthesis, structure, and properties of switchable cross-conjugated 1,4-diaryl-1,3-butadiynes based on 1,8-bis(dimethylamino)naphthalene

• Semyon V. Tsybulin,
• Ekaterina A. Filatova,
• Alexander F. Pozharskii,
• Valery A. Ozeryanskii and
• Anna V. Gulevskaya

Beilstein J. Org. Chem. 2023, 19, 674–686, doi:10.3762/bjoc.19.49

• systems; 1,4-diaryl-1,3-butadiynes; donor–acceptor systems; Glaser–Hay reaction; Introduction π-Conjugated oligomers and polymers attracted considerable attention from the very start as a promising class of semiconductors, chemosensors, and various electronic devices [1][2]. Although silicon and

Enolates ambushed – asymmetric tandem conjugate addition and subsequent enolate trapping with conventional and less traditional electrophiles

• Péter Kisszékelyi and
• Radovan Šebesta

Beilstein J. Org. Chem. 2023, 19, 593–634, doi:10.3762/bjoc.19.44

• all possess helpful and, to an extent, specific reactivity characteristics. Interesting boron and silicon enolates can be generated by asymmetric conjugate boration [16], or silylation [17]. From several potentially catalytically active transition metals, copper combines beneficial properties for both

C3-Alkylation of furfural derivatives by continuous flow homogeneous catalysis

• Grédy Kiala Kinkutu,
• Catherine Louis,
• Myriam Roy,
• Juliette Blanchard and
• Julie Oble

Beilstein J. Org. Chem. 2023, 19, 582–592, doi:10.3762/bjoc.19.43

• with good productivity. Alkenes without silicon in the vinyl position seemed much less reactive, such as a vinylacetal, a hindered olefin (3,3-dimethyl-1-butene), or styrene. In these cases, functionalized furfurals were not isolated. In contrast, norbornene, which has a more reactive double bond due

Catalytic aza-Nazarov cyclization reactions to access α-methylene-γ-lactam heterocycles

• Bilge Banu Yagci,
• Selin Ezgi Donmez,
• Onur Şahin and
• Yunus Emre Türkmen

Beilstein J. Org. Chem. 2023, 19, 66–77, doi:10.3762/bjoc.19.6

• analysis of lactam 19l. In order to shed light on the details of the reaction mechanism, we have performed carefully designed mechanistic studies which consist of experiments on the effect of β-silicon stabilization, the alkene geometry of the α,β-unsaturated acyl chloride reactants, and adventitious water

• on the success of the catalytic aza-Nazarov reaction. Keywords: α-methylene-γ-lactam; aza-Nazarov reaction; β-silicon effect; heterocycles; intramolecular cyclization; Introduction The rapid construction of aliphatic heterocycles from acyclic building blocks via cyclization or cycloaddition

• ) group via the β-silicon stabilization effect [36][37][38] as supported by computational studies [35]. The desilylation of intermediate 9 with the chloride of another molecule of 8 would result in the formation of final aza-Nazarov product 7 along with TMSCl (Scheme 1d). Five-membered nitrogen

Inclusion complexes of the steroid hormones 17β-estradiol and progesterone with β- and γ-cyclodextrin hosts: syntheses, X-ray structures, thermal analyses and API solubility enhancements

• Alexios I. Vicatos,
• Zakiena Hoossen and
• Mino R. Caira

Beilstein J. Org. Chem. 2022, 18, 1749–1762, doi:10.3762/bjoc.18.184

• radiation (λ = 1.5406 Å) with the X-ray generator set at 30 kV and 10 mA. All samples were lightly ground (to minimise the effects of preferred orientation) and placed on a silicon zero-background sample holder. The scanning range was 4o – 40o 2θ with a step size of 0.0164o and a primary beam path slit of

Modular synthesis of 2-furyl carbinols from 3-benzyldimethylsilylfurfural platforms relying on oxygen-assisted C–Si bond functionalization

• Sebastien Curpanen,
• Per Reichert,
• Gabriele Lupidi,
• Giovanni Poli,
• Julie Oble and
• Alejandro Perez-Luna

Beilstein J. Org. Chem. 2022, 18, 1256–1263, doi:10.3762/bjoc.18.131

• carbinols from renewable feedstock. Keywords: biomass; copper; cyclic siloxanes; 2-furyl carbinols; silicon; Introduction Progress towards the use of nonedible renewable feedstock to replace fossil resources as starting material for high-value chemicals is an important endeavor of modern synthesis [1][2

• of electrophiles to deliver product D, resulting from the overall C2–Si functionalization (Scheme 3, top) [24][25]. The key to the viability of this process is the formation of pentavalent silicon intermediate B. This suggested that a related pentavalent intermediate F could be similarly accessible

• of benzaldehyde led to the formation of adduct 14 (in 75% yield), which arose from the addition of a benzyl carbanion 17 to benzaldehyde. The generation of such a nucleophile strongly suggests the formation of pentavalent silicon intermediate 15 [27], which then produced a (stabilized) benzylic

Electrochemical formal homocoupling of sec-alcohols

• Kosuke Yamamoto,
• Kazuhisa Arita,
• Masashi Shiota,
• Masami Kuriyama and
• Osamu Onomura

Beilstein J. Org. Chem. 2022, 18, 1062–1069, doi:10.3762/bjoc.18.108

• catalytic amount of transition-metal reductants have been developed, but stoichiometric silicon electrophiles and co-reductants such as Zn were commonly required to complete the catalytic cycle [14]. More recently, visible light-mediated pinacol coupling reactions have been disclosed by several groups [15

Thiophene/selenophene-based S-shaped double helicenes: regioselective synthesis and structures

• Mengjie Wang,
• Lanping Dang,
• Wan Xu,
• Zhiying Ma,
• Liuliu Shao,
• Guangxia Wang,
• Chunli Li and
• Hua Wang

Beilstein J. Org. Chem. 2022, 18, 809–817, doi:10.3762/bjoc.18.81

• thiahelicene, a class of typical heterohelicenes, has led to the preparation of symmetric thiophene-based [5]-, [7]-, [9]-, and [11]helicenes [9][10][11][12][13][14][15][16], unsymmetric thiophene-based [7]helicenes [17], and thiophene-based double helicenes with spiro-silicon atoms [18], “saddle” formed 8π

• and DH-1–3. Molecular structures and side view for DH-1 and DH-2. A and B are molecular structures for DH-1 and DH-2. C and D are side views for DH-1 and DH-2. Carbon, sulfur, selenium, and silicon atoms are depicted with thermal ellipsoids set at the 30% probability level and all hydrogen atoms are

Inductive heating and flow chemistry – a perfect synergy of emerging enabling technologies

• Conrad Kuhwald,
• Sibel Türkhan and
• Andreas Kirschning

Beilstein J. Org. Chem. 2022, 18, 688–706, doi:10.3762/bjoc.18.70

• application for heating large metallic objects and workpieces. It is used for bending tubes, bonding, welding, sintering, and annealing of metals and alloys [11]. In addition to steel and alloys, glass or silicon are also heated or melted under inductive heating conditions [12]. In the last decade, inductive

• enable rapid heating of inductive materials such as steel or copper, or fixed-bed materials composed of steel beads as well as superparamagnetic nanoparticles in an oscillating electromagnetic field. Kirschning and co-workers introduced nanostructured particles based on Fe2O3/Fe3O4 coated with silicon

• consisting of O-allylation and Claisen rearrangement for the continuous synthesis of 2-allyl-4,6-difluorophenol (SiC = silicon carbide) [52]. Continuous flow reactions and comparison with batch reaction (oil bath). A. Pd-catalyzed transfer hydrogenations using ethanol in cyclohexene [53], B. multicomponent