The effect of neighbouring group participation and possible long range remote group participation in O-glycosylation

• Rituparna Das and
• Balaram Mukhopadhyay

Beilstein J. Org. Chem. 2025, 21, 369–406, doi:10.3762/bjoc.21.27

• phenol 16 and acceptor 19 to the anomeric position, thereby, making it suitable for glycoconjugate formation. They also reported the glycosylations leading to disaccharide 20 formation in solvent free conditions in significant 1,2-trans selectivity. This study holds the potential in improving the various

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

• the radical cation iPr2NEt•+ (iPr2NEt/iPr2NEt•+ = +0.72 V vs SCE) and the reduction of O2 by the reduced photocatalyst, forming the superoxide radical anion O2•− (O2/O2•− = −0.57 V vs SCE). This latter can then react with arylboronic acids 59 to give, after hydrolysis, phenol derivatives 60. Other

Streamlined modular synthesis of saframycin substructure via copper-catalyzed three-component assembly and gold-promoted 6-endo cyclization

• Asahi Kanno,
• Ryo Tanifuji,
• Satoshi Yoshida,
• Sota Sato,
• Saori Maki-Yonekura,
• Kiyofumi Takaba,
• Jungmin Kang,
• Kensuke Tono,
• Koji Yonekura and
• Hiroki Oguri

Beilstein J. Org. Chem. 2025, 21, 226–233, doi:10.3762/bjoc.21.14

• three base pairs, predominantly 5’-GGC-3’ and 5’-GGG-3’ [12][13]. Notably, a bis-phenol type unnatural analog 3, composed of the C5 deoxy A-ring bearing a phenolic hydroxy group at C8, presumably as a HB donor upon interaction with nucleic acids, exhibits superior DNA alkylation capability compared to

• coupling of alkyne 8, THIQ segment 9, and benzaldehyde would enable convergent assembly of the building blocks to produce 10 [43][44][45][46]. Removal of the cyclic acetal in 10 followed by Strecker-type conversion leading to an α-amino nitrile would enable tandem intramolecular cyclization with phenol to

• a phenol moiety. The final step is assumed to be facilitated by the release of the ring distortion of the benzofuran system. Overall, triggered by the gold(I)-promoted 6-endo hydroamination between the 2,3-diaminobenzofuran and the alkyne in 11, dehydrogenative oxidation of the resulting 12 to form

Quantifying the ability of the CF₂H group as a hydrogen bond donor

• Matthew E. Paolella,
• Daniel S. Honeycutt,
• Bradley M. Lipka,
• Jacob M. Goldberg and
• Fang Wang

Beilstein J. Org. Chem. 2025, 21, 189–199, doi:10.3762/bjoc.21.11

• the HB donor. As shown in Figure 3B, in our hands, the Kd of the phenol–Reichardt's dye HB adduct determined is consistent with the reported value [52]. Some of our other results, however, were puzzling. For example, according to our titration data, 1a is a better HB donor than 12. This observation is

• constructs. Although many of the CF2H HB donors studied here can promote relatively strong hydrogen bonding interactions with n-Bu3PO, even the strongest CF2H HB donor (3b) is still 30 times weaker than phenol (10), corresponding to about a 2 kcal/mol reduction in binding energy at 25 °C. These results

Recent advances in organocatalytic atroposelective reactions

• Henrich Szabados and
• Radovan Šebesta

Beilstein J. Org. Chem. 2025, 21, 55–121, doi:10.3762/bjoc.21.6

• organocatalyst C21 was studied in 2019 (Scheme 21) [44]. A broad range of aniline and phenol substrates was studied. The best results were accomplished with products containing a Boc-protected amino group on the aniline or 2-aminonaphthalene frame (66a–g), achieving very good yields and excellent

• the final step of the reaction, ring opening by the C–C bond cleavage yields the desired product 203. The first phosphoric acid C39-catalyzed asymmetric cycloaddition–elimination cascade reaction of 2-naphthol or phenol enamide derivatives 204 with azonaphthalenes 205 was done by Xu et al. in 2021

Germanyl triazoles as a platform for CuAAC diversification and chemoselective orthogonal cross-coupling

• John M. Halford-McGuff,
• Thomas M. Richardson,
• Aidan P. McKay,
• Frederik Peschke,
• Glenn A. Burley and
• Allan J. B. Watson

Beilstein J. Org. Chem. 2024, 20, 3198–3204, doi:10.3762/bjoc.20.265

• -coupling to give 32 or chemoselective Negishi coupling to give 33 [74]. Finally, BPin 21 could be oxidised to the phenol derivative 34 or cross-coupled with piperidine under Chan–Lam conditions to give the aniline derivative 35 in good yield [75]. Conclusion In summary, we have developed a general method

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

• radical–Ru(III)(OH) intermediate, which provides the cationic intermediate from phenol via electron transfer. The reaction of cation D with TBHP results in the mixed peroxide 87 [84]. However, this mechanism was later doubted based on the experimental data of [Rh2(cap)4]-catalyzed peroxidation of phenols

Recent advances in transition-metal-free arylation reactions involving hypervalent iodine salts

• Ritu Mamgain,
• Kokila Sakthivel and
• Fateh V. Singh

Beilstein J. Org. Chem. 2024, 20, 2891–2920, doi:10.3762/bjoc.20.243

• reaction that results in the formation of diaryl ethers. Diaryl ethers are important structural motifs in pharmaceuticals and agrochemicals due to their diverse biological activities. Since the 1950s, one of the most used methods for the synthesis of diaryl ethers involves the reaction of phenol with

• K2CO3 at 55 °C to yield the corresponding products 62 in good to excellent yield (Scheme 25) [76]. It was observed that both electronic as well as steric effects on the aryl electrophile and phenol nucleophile were well tolerated. Further, this study was used for the one-pot synthesis of diaryl ethers

• , and iodination of the gemfibrozil aromatic ring by reacting them with the corresponding nucleophiles. Notably, reactions with phenol, thiophenol and benzoic acid using salts 71 in the presence of t-BuOK led to the corresponding products 72 with 61%, 69%, and 77% yields, respectively (Scheme 28). These

Copper-catalyzed yne-allylic substitutions: concept and recent developments

• Shuang Yang and
• Xinqiang Fang

Beilstein J. Org. Chem. 2024, 20, 2739–2775, doi:10.3762/bjoc.20.232

• substituted pybox ligand (Scheme 28, 26a–m). The thiophene unit of the carbonate could also be replaced by benzothiophene (Scheme 28, 26h) or furan (Scheme 28, 26m), and pyrrole (Scheme 28, 26j), phenol (Scheme 28, 26k); coumarin derivative (Scheme 28, 26n), and dibenzylamine (Scheme 28, 24a) could also

Transition-metal-free decarbonylation–oxidation of 3-arylbenzofuran-2(3H)-ones: access to 2-hydroxybenzophenones

• Bhaskar B. Dhotare,
• Seema V. Kanojia,
• Chahna K. Sakhiya,
• Amey Wadawale and
• Dibakar Goswami

Beilstein J. Org. Chem. 2024, 20, 2655–2667, doi:10.3762/bjoc.20.223

• the carbonyl and the phenol residue is weakened. A similar phenomenon has been reported for 4′-substituted- 2-hydroxybenzophenones [6]. On the contrary, a strong electron-withdrawing group viz. –F at the 4'-position (4fd) rendered the compound to be a poor UV-protector. It was also observed that the

• residue (8.2 g), which was further characterized using 1H NMR. General procedure for the synthesis of 3-arylbenzofuran-2(3H)-ones (3aa–ma). 3-Arylbenzofuran-2(3H)-ones 3aa–ma were synthesized using a method previously reported by us [20]. A mixture of SbCl3 (1.5 mmol), phenol/substituted phenol 1a–m (5

The scent gland composition of the Mangshan pit viper, Protobothrops mangshanensis

• Jonas Holste,
• Paul Weldon,
• Donald Boyer and
• Stefan Schulz

Beilstein J. Org. Chem. 2024, 20, 2644–2654, doi:10.3762/bjoc.20.222

• components, carboxylic acids, alcohols, glycerol ethers, amides, and volatile compounds such as phenol, benzaldehyde, or indole were present (Figure 1 and Table 1). While some of these compounds were easily identified, a group of diketopiperazines (DKPs) and a series of unknown putative carboxylic acids (A–F

Efficient modification of peroxydisulfate oxidation reactions of nitrogen-containing heterocycles 6-methyluracil and pyridine

• Alfiya R. Gimadieva,
• Yuliya Z. Khazimullina,
• Aigiza A. Gilimkhanova and
• Akhat G. Mustafin

Beilstein J. Org. Chem. 2024, 20, 2599–2607, doi:10.3762/bjoc.20.219

• : oxidation; 6-methyluracil; peroxydisulfate; phthalocyanine catalysts; pyridine; Introduction The Elbs and Boyland–Sims peroxydisulfate oxidation reactions offer a convenient means of introducing the hydroxy function into phenols and aromatic amines [1]. The oxidation of phenol using peroxydisulfate was

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

• -pyridyl)phenol (23) as an activator, 3 equivalents of HFIP and a slightly different catalyst, 3,3’-bis(3,5-bis(trifluoromethyl)phenyl)-BINOL 21 at 20 mol % loading (Scheme 5). Interestingly, the reaction showed an opposite trend and worked better with Z-geranylboronic acid (14). The scope was tested over

Heterocycle-guided synthesis of m-hetarylanilines via three-component benzannulation

• Andrey R. Galeev,
• Maksim V. Dmitriev,
• Alexander S. Novikov and
• Andrey N. Maslivets

Beilstein J. Org. Chem. 2024, 20, 2208–2216, doi:10.3762/bjoc.20.188

• condensation by introducing additional functional groups into the amine moiety (Figure 3). Substituted arylamines bearing alcohol (3ae), phenol (3ad), alkene (3bi), dimethyl acetal (3bj) functionality can be accessed in good yields. Reaction of 1,3-diketone 1a with a non-amidine type heterocyclic amine, 3

A new platform for the synthesis of diketopyrrolopyrrole derivatives via nucleophilic aromatic substitution reactions

• Vitor A. S. Almodovar and
• Augusto C. Tomé

Beilstein J. Org. Chem. 2024, 20, 1933–1939, doi:10.3762/bjoc.20.169

• aromatic substitution; phenol; thiol; Introduction Diketopyrrolopyrroles (DPPs) are a class of organic pigments discovered by serendipity in the 1970s [1][2]. Generally, N-unsubstituted DPP derivatives exhibit high melting points, low solubility in most solvents, and strong absorption in the visible

• effective nucleophile. So, in this case, Cs2CO3 was employed as the base. The reaction of DPP 2 with methyl 4-hydroxybenzoate yielded compounds 3d and 4d in 56% and 14% yield, respectively. When reacting with 4-(2,4,4-trimethylpentan-2-yl)phenol, the disubstituted compound 3e was obtained in 63% yield. In

Synthesis of polycyclic aromatic quinones by continuous flow electrochemical oxidation: anodic methoxylation of polycyclic aromatic phenols (PAPs)

• Hiwot M. Tiruye,
• Solon Economopoulos and
• Kåre B. Jørgensen

Beilstein J. Org. Chem. 2024, 20, 1746–1757, doi:10.3762/bjoc.20.153

• oxidation forms the p-quinones when possible. However, the o-quinones are formed in good yields from substrates where the para-position of the phenol is part of the further polycyclic aromatic skeleton. The products could be separated from the supporting electrolyte by dispersing the solids in ethyl acetate

• 0.1 V/s in 0.1 M [NBu4] [PF6] in MeCN and UV–vis spectra of PAPs in DCM (≈10−5 M). A, B: naphthols 1a,b. C, D: chrysenols 3a–c. E, F: phenanthrols 6a–c. Resonance structures of the phenoxonium cation formed from 2-chrysenol (3a). Formation of phenoxonium cation in the anodic oxidation of phenol

Syntheses and medicinal chemistry of spiro heterocyclic steroids

• Laura L. Romero-Hernández,
• Ana Isabel Ahuja-Casarín,
• Penélope Merino-Montiel,
• Sara Montiel-Smith,
• José Luis Vega-Báez and
• Jesús Sandoval-Ramírez

Beilstein J. Org. Chem. 2024, 20, 1713–1745, doi:10.3762/bjoc.20.152

• androgenic activity. Poirier’s group reported two methodologies to prepare spiromorpholin-3-ones from a β-amino alcohol functionality [39]. Spiro compounds were synthesized starting from estrone, in which the phenol group was protected as a methoxymethyl ether. Then, the protected compound was subjected to

Chemo-enzymatic total synthesis: current approaches toward the integration of chemical and enzymatic transformations

• Ryo Tanifuji and
• Hiroki Oguri

Beilstein J. Org. Chem. 2024, 20, 1693–1712, doi:10.3762/bjoc.20.151

• bisorbicillinoid family. Substrate 33 for SorbC-catalyzed enzymatic transformation was synthesized in 3 steps from phenol 35 via formylation and subsequent reduction to introduce a methyl group, followed by a Friedel–Crafts acylation with 36 (Scheme 4B) [39][40]. The in vitro enzymatic transformation of 33 by

• phenol 46 yields moracin C (47). As the final steps in the biosynthesis of 3, oxidation of the prenyl group of 47 to diene 48 and the subsequent DA reaction with dienophile 44 should theoretically be catalyzed by oxidase and Diels–Alderase, respectively. However, despite effort over several decades

• utilizing the successfully overexpressed Diels–Alderase, MaDA (Scheme 5C). The chemical synthesis of 54, tri-O-acetylated precursor of the diene component 48, commenced from phenol 50. Iodination and O-acetylations of 50 followed by coupling with phosphorus ylide 51 afforded aryl iodide 52. Subsequent

Polymer degrading marine Microbulbifer bacteria: an un(der)utilized source of chemical and biocatalytic novelty

• Weimao Zhong and
• Vinayak Agarwal

Beilstein J. Org. Chem. 2024, 20, 1635–1651, doi:10.3762/bjoc.20.146

• between polybrominated phenol biosynthetic enzymes in diverse marine microbial genera will undoubtedly complement the wide distribution of these natural products in the marine metabolome. All marine bacteria discussed in this section are members of commensal or symbiotic microbiomes of marine

Supramolecular assemblies of amphiphilic donor–acceptor Stenhouse adducts as macroscopic soft scaffolds

• Ka-Lung Hung,
• Leong-Hung Cheung,
• Yikun Ren,
• Ming-Hin Chau,
• Yan-Yi Lam,
• Takashi Kajitani and
• Franco King-Chi Leung

Beilstein J. Org. Chem. 2024, 20, 1590–1603, doi:10.3762/bjoc.20.142

• calcium chloride solution, the obtained DAn macroscopic scaffold was washed three times with fresh Milli-Q water, followed by the addition of 0.5 mL of a growth medium consisting of minimum essential medium (MEM α, no phenol red, Gibco), 10% fetal bovine serum (FBS, Gibco), and 1% antibiotic–antimycotic

Mining raw plant transcriptomic data for new cyclopeptide alkaloids

• Draco Kriger,
• Michael A. Pasquale,
• Brigitte G. Ampolini and
• Jonathan R. Chekan

Beilstein J. Org. Chem. 2024, 20, 1548–1559, doi:10.3762/bjoc.20.138

• alkaloids, containing both Ziziphus and Ceanothus genera. In addition to the subclass defining Tyr-phenol-O to carbon linkage, the cyclopeptide alkaloids of this family are typically oxidatively decarboxylated and N-methylated (Figure 1, adouetine X and Figure 3, ceanothine B) [19][20][21]. Our

• (Figure 3 and Supporting Information File 2). Malvaceae family The Malvaceae family contains Hibiscus syriacus (Rose of Sharon), the only known producer of hibispeptin-type burpitides (Figure 3, hibispeptin B) [24][25]. These molecules contain a C–C linkage between the phenol derived from tyrosine and the

Synthesis of 2-benzyl N-substituted anilines via imine condensation–isoaromatization of (E)-2-arylidene-3-cyclohexenones and primary amines

• Lu Li,
• Na Li,
• Xiao-Tian Mo,
• Ming-Wei Yuan,
• Lin Jiang and
• Ming-Long Yuan

Beilstein J. Org. Chem. 2024, 20, 1468–1475, doi:10.3762/bjoc.20.130

• products. Interestingly, when the 2-arylidene-3-cyclohexenones bearing a strong electron-withdrawing group take part in the reaction, a base-promoted phenol formation via self-tautomerization of cyclohexenones emerges as a competing reaction pathway (Scheme 1, this work). Results and Discussion The present

• pathway appeared to proceed via self-tautomerization, since 2-benzylphenol 5f was separated in 43% yield along with only 23% yield of normal product 4fa. When 4-CN substituted 3-cyclohexanone was investigated, phenol 5o was isolated exclusively. This was probably due to the significantly enhanced acidity

Domino reactions of chromones with activated carbonyl compounds

• Peter Langer

Beilstein J. Org. Chem. 2024, 20, 1256–1269, doi:10.3762/bjoc.20.108

• adjacent to the phenol moiety resulted in formation of intermediate L and lactonization gave the final products. The regioselectivity of the cyclization can be explained by steric hindrance of the carbonyl group adjacent to the 2-nitrophenyl moiety containing an ortho-substituent. Interestingly, in case of

• formation of products 27, the cyclization proceeded by attack of the methylene carbon to the carbonyl group adjacent to the phenol moiety (intermediate N). This might be explained by the fact that the carbonyl adjacent to the perfluoroalkyl group exists as a hydrate which reduces significantly its

Auxiliary strategy for the general and practical synthesis of diaryliodonium(III) salts with diverse organocarboxylate counterions

• Naoki Miyamoto,
• Daichi Koseki,
• Kohei Sumida,
• Elghareeb E. Elboray,
• Naoko Takenaga,
• Ravi Kumar and
• Toshifumi Dohi

Beilstein J. Org. Chem. 2024, 20, 1020–1028, doi:10.3762/bjoc.20.90

• modifying their physical properties, and stability and controlling the reactivity of arylation processes, as demonstrated in various studies [9][10]. For instance, the Gaunt group reported that the use of a fluoride counterion in diaryliodonium(III) salt can trigger phenol O-arylation by activating the

• phenolic O–H group with a fluoride anion [11]. Additionally, Muñiz et al. found that the acetate counterion was more effective than chloride, hexafluorophosphate, and trifluoromethane sulfonate for the borylation of diaryliodonium(III) salts [12]. Recently, our group has developed a new method for phenol O

• -arylation using aryl(2,4,6-trimethoxyphenyl)iodonium(III) acetates [13]. In this process, the acetate ligand acted as a base to activate the phenol group and positioned it in proximity to accomplish the smooth SNAr reaction. The synthesis of diaryliodonium(III) salts with various counterions, such as

Spin and charge interactions between nanographene host and ferrocene

• Akira Suzuki,
• Yuya Miyake,
• Ryoga Shibata and
• Kazuyuki Takai

Beilstein J. Org. Chem. 2024, 20, 1011–1019, doi:10.3762/bjoc.20.89

• photoelectron spectroscopy (XPS), Raman spectroscopy, Fourier-transform infrared (FTIR) spectroscopy, magnetic susceptibility, and electron-spin resonance (ESR). Experimental Commercially available ACFs (Kuraray, FR-20), of which the precursor was a phenol-resin, were pre-heat-treated in a glass tube at 200 °C