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

• alcohols and aldehydes [11] and through [2 + 3] cycloaddition of azomethine ylides and carbonyl dipolarophiles [12]. Recently, the [2 + 3] annulation of aldehydes and donor–acceptor dialkyl 2-aryl-1-sulfonylaziridine-2,2-dicarboxylates, which generate azomethine ylides, has been developed for the synthesis

Recent advances in synthetic approaches for bioactive cinnamic acid derivatives

• Betty A. Kustiana,
• Galuh Widiyarti and
• Teni Ernawati

Beilstein J. Org. Chem. 2025, 21, 1031–1086, doi:10.3762/bjoc.21.85

• -acylation of cinnamic acid above. 2.2.1 Alcohol oxidation: Kapdi and co-workers (2019) reported Pd-colloids-catalyzed esterification via Ag2O-catalyzed alcohol oxidation. Herein, cinnamyl alcohols were oxidized to the corresponding cinnamaldehydes catalyzed by Ag2O, followed by oxidative addition to Pd via

• 153 and 154 to give the corresponding esters 44 and 152 driven by MeOH attack (Scheme 47) [87]. Hu and co-workers (2021) developed an N-doped carbon black-supported PdBi bimetallic catalyst (Pd5Bi5/NCB) for the oxidative esterification of cinnamyl alcohols via hemiacetal 156 oxidation (Scheme 48A) [88

• (2021) developed a Cr-based catalyst stabilized by a pentaerythritol-decorated Anderson-type polyoxometalate, [N(C4H9)4]3[CrMo6O18(OH)3C{(OCH2)3CH2-OH}] (cat 3), to catalyze the oxidative esterification of cinnamyl alcohols using H2O2. The reaction proceeds also via a hemiacetal intermediate 155 (Scheme

Biobased carbon dots as photoreductants – an investigation by using triarylsulfonium salts

• Valentina Benazzi,
• Arianna Bini,
• Ilaria Bertuol,
• Mariangela Novello,
• Federica Baldi,
• Matteo Hoch,
• Alvise Perosa and
• Stefano Protti

Beilstein J. Org. Chem. 2025, 21, 1024–1030, doi:10.3762/bjoc.21.84

• ); triarylsulfonium salts; visible light; Introduction Carbon dots (CDs) are a class of zero-dimensional carbon-based semiconducting nanoparticles bearing on the surface a wide range of functional groups, such as carboxylic acids, alcohols, and amines, that garnered significant attention in the last decade among the

Harnessing tethered nitreniums for diastereoselective amino-sulfonoxylation of alkenes

• Shyam Sathyamoorthi,
• Appasaheb K. Nirpal,
• Dnyaneshwar A. Gorve and
• Steven P. Kelley

Beilstein J. Org. Chem. 2025, 21, 947–954, doi:10.3762/bjoc.21.78

• compatible with our optimized protocols (Table 4). Earlier in the project, we had focused exclusively on substrates derived from trans-homo-allylic alcohols. We were thus pleased to find that a substrate synthesized from cis-3-hexen-1-ol was equally compatible and gave product in an excellent yield and

• synthesized in one pot with good yields and excellent diastereoselectivities (Table 4, entries 5 and 9). Surprisingly, carbamate substrates derived from di-substituted allylic alcohols (Figure 1) invariably failed to give the desired amino-sulfonoxylated products. With these substrates, 1H NMR analysis of the

A convergent synthetic approach to the tetracyclic core framework of khayanolide-type limonoids

• Zhiyang Zhang,
• Jialei Hu,
• Hanfeng Ding,
• Li Zhang and
• Peirong Rao

Beilstein J. Org. Chem. 2025, 21, 926–934, doi:10.3762/bjoc.21.75

• 4.4:1 mixture of regioisomeric alcohols with the desired isomer being the major component, presumably due to the considerable steric hindrance from the quaternary carbon at C4. However, decagram-scale separation of these two isomers by chromatography proved troublesome. Fortunately, the distinct

• reactivity of those two alcohols toward oxidation allowed for the selective conversion of desired alcohol to ketone 24 using PCC, producing a 50% overall yield, while the recovered undesired alcohol could be reverted to 21 by Swern oxidation. Direct enol triflation (Et3N/Tf2O, NaH/PhNTf2, DTBMP/Tf2O, etc

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

• and n-BuLi, followed by a reaction with ZnCl2 at room temperature. The product is then hydrolyzed with a NaOH solution of H2O2 to yield amino alcohols. The mechanism involves the formation of borate intermediate Int-79 from substrate 83 under the action of CH2BrLi. This is followed by an N-1,2

Recent advances in the electrochemical synthesis of organophosphorus compounds

• Babak Kaboudin,
• Milad Behroozi,
• Sepideh Sadighi and
• Fatemeh Asgharzadeh

Beilstein J. Org. Chem. 2025, 21, 770–797, doi:10.3762/bjoc.21.61

• first due to its lowest oxidation potential among the species. In 2024, Zhu et al. [63] reported an electrochemical transition-metal and additive-free synthesis of phosphorylated propargyl alcohols at room temperature. The reaction is carried out in an undivided cell using glassy carbon (GC) as an anode

• corresponding phosphorylated propargyl alcohols (Scheme 19). The reaction yield showed that this method is not sensitive to electron-withdrawing or electron-donating groups at different positions on the aromatic ring. Most likely, the 3-substituted pyridine substrate and the enynes with nitro or carbonyl groups

• . In this method, they have reported an electrochemical reaction of alcohols (aliphatic and aromatic) and diphenylphosphine in an undivided cell, using carbon and nickel electrodes as the anode and cathode, respectively, at a constant current for 4 h in the presence of cesium carbonate as a base

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

• ; hydrazones; isocyanides; Introduction Catalytic applications of non-toxic earth abundant metals like calcium are currently on the rise [1][2][3][4]. Prominent recent examples that witness the versatility of calcium catalysis include calcium-catalyzed amination of π-activated alcohols [5], the Beckmann

• of alcohols as additives has a negative effect on both yield and enantioselectivity. The enantioselectivity was generally low (Table 2, entries 4–9) and with preference for the S-configured hydrocyanide employing the pre-formed Ca complex 6. In addition, product 2 was obtained with absolute

Origami with small molecules: exploiting the C–F bond as a conformational tool

• Patrick Ryan,
• Ramsha Iftikhar and
• Luke Hunter

Beilstein J. Org. Chem. 2025, 21, 680–716, doi:10.3762/bjoc.21.54

• scaffolds – alkanes – then we will progress to ethers, alcohols, sugars, amines (and their derivatives), carbonyl compounds, peptides, and finally sulfur-containing compounds. By arranging the material in this way, we hope that newcomers to the field might be able to readily envisage ways to apply these

• suffers from Lewis F···O repulsion. In contrast, the ga and ag conformers have less hyperconjugation but also less F···O repulsion, and are less polar. Since all three conformers are close in energy, the difluoroethyl ether moiety in 51 can be considered to have chameleonic polarity. 3 Alcohols We now

• progress from ethers (section 2) to a closely related class of molecules, namely, the alcohols. The focus here in section 3 will be mostly on simple examples; more complex poly-ol examples will be discussed in section 4 (sugars). Taking the example of a simple alcohol such as ethanol, consider what happens

Asymmetric synthesis of fluorinated derivatives of aromatic and γ-branched amino acids via a chiral Ni(II) complex

• Maurizio Iannuzzi,
• Thomas Hohmann,
• Michael Dyrks,
• Kilian Haoues,
• Katarzyna Salamon-Krokosz and
• Beate Koksch

Beilstein J. Org. Chem. 2025, 21, 659–669, doi:10.3762/bjoc.21.52

• iodides can be efficiently synthesized in gram-scale from the respective fluorinated alcohols using alkyl nonaflates as a key intermediate [13]. Based on these results, 3,3,3-trifluoro-2-methylpropan-1-ol (8) was selected as the starting material. We started our efforts by screening the reaction

Recent advances in allylation of chiral secondary alkylcopper species

• Minjae Kim,
• Gwanggyun Kim,
• Doyoon Kim,
• Jun Hee Lee and
• Seung Hwan Cho

Beilstein J. Org. Chem. 2025, 21, 639–658, doi:10.3762/bjoc.21.51

• reaction, catalyzed by a sulfonate-containing chiral NHC–Cu complex, proceeded with excellent chemo-, regio- (SN2'-), diastereo-, and enantioselectivity to afford homoallylic boronates 36. The resulting organoboron compounds could be oxidized to secondary homoallylic alcohols, providing an alternative to

• showed a broad scope, tolerating both 1,1-diborylalkanes with N-tosyl-protected amines and TBS-protected alcohols, as well as substrates containing alkenes and alkynes. Various allylic bromides 46 with electron-rich and electron-deficient aryl substituents worked well, giving homoallylic boronic esters

Formaldehyde surrogates in multicomponent reactions

• Cecilia I. Attorresi,
• Javier A. Ramírez and
• Bernhard Westermann

Beilstein J. Org. Chem. 2025, 21, 564–595, doi:10.3762/bjoc.21.45

• devoted to dimethyl sulfoxide, dihalomethanes, hexamethylene tetramine, and glyoxylates as C1-building blocks, substituting formaldehyde. Review Methanol as a source of formaldehyde There are several reports on the use of alcohols under oxidative conditions as aldehyde surrogates in Ugi and Passerini

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

• , Chiba 263-8522, Japan 10.3762/bjoc.21.43 Abstract β-Amino cyanoesters are important scaffolds because they can be transformed into useful chiral amines, amino acids, and amino alcohols. Halogen bonding, which can be formed between halogen atoms and electron-rich chemical species, is attractive because

• alcohols [38]. In this context, their asymmetric syntheses are important and have also been researched mainly using chiral catalysts [39][40]. Previously, the Mannich reaction has been applied in the construction of contiguous stereogenic centers (Figure 2). In 2005, Jørgensen and co-workers reported the

Vinylogous functionalization of 4-alkylidene-5-aminopyrazoles with methyl trifluoropyruvates

• Judit Hostalet-Romero,
• Laura Carceller-Ferrer,
• Gonzalo Blay,
• Amparo Sanz-Marco,
• José R. Pedro and
• Carlos Vila

Beilstein J. Org. Chem. 2025, 21, 533–540, doi:10.3762/bjoc.21.41

• between 4-alkylidene-5-aminopyrazoles and alkyl trifluoropyruvates leading to highly functionalized tertiary alcohols bearing a trifluoromethyl group and a pyrazole ring is presented. The corresponding trifluoromethyl alcohols are obtained in moderate to good yields (up to 80%) and high

• diastereoselectivity (up to 7:1). Keywords: alcohols; diastereoselectivity; nitrogen heterocycles; pyrazoles; vinylogous reaction; Introduction Vinylogy refers to the transmission of electronic effects through a conjugated π-system, enabling the extension of a functional group's nucleophilic or electrophilic

• compounds is a significant and important reaction for the selective synthesis of homoallylic alcohols in an efficient and sustainable way [2][3]. As carbonyl compounds, alkyl trifluoropyruvates [4][5] are an interesting class of compounds that have been used in addition reactions of different nucleophiles

Synthesis of the aggregation pheromone of Tribolium castaneum

• Biyu An,
• Xueyang Wang,
• Ao Jiao,
• Qinghua Bian and
• Jiangchun Zhong

Beilstein J. Org. Chem. 2025, 21, 510–514, doi:10.3762/bjoc.21.38

• )-10. Synthesis of the aggregation pheromone of Tribolium castaneum. Supporting Information Supporting Information File 6: General information, synthesis of compounds 1–12, research on the optical purity of chiral alcohols (R)- and (S)-4, and copies of 1H, 13C and 19F NMR spectra. Funding This

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

• . First, the alkyl handles bearing a primary hydroxy group were introduced and then converted into the electrophile of choice. More specifically, to furnish compounds 4b–d, precursor 9 was treated with the corresponding amino alcohols in the presence of a desiccant. The imines formed were subjected to

• mild reduction with methanolic sodium borohydride. Upon purification by reversed-phase chromatography using aqueous hydrobromic acid as eluent (0.5% in H2O), a considerable fraction of the alcohols was already converted to the desired bromides 4c,d. Only in the case of 4b, no deoxygenative bromination

Organocatalytic kinetic resolution of 1,5-dicarbonyl compounds through a retro-Michael reaction

• James Guevara-Pulido,
• Fernando González-Pérez,
• José M. Andrés and
• Rafael Pedrosa

Beilstein J. Org. Chem. 2025, 21, 473–482, doi:10.3762/bjoc.21.34

• processes with low catalyst loading. It involves the kinetic resolution of alcohols, amines, and esters using chiral phosphoric acids [6][7][8][9][10][11][12][13] and sulfoximines with enals using chiral N-heterocyclic carbene (NHC) catalysts [14]. Additionally, these processes have been conducted using

Photomechanochemistry: harnessing mechanical forces to enhance photochemical reactions

• Francesco Mele,
• Ana M. Constantin,
• Andrea Porcheddu,
• Raimondo Maggi,
• Giovanni Maestri,
• Nicola Della Ca’ and
• Luca Capaldo

Beilstein J. Org. Chem. 2025, 21, 458–472, doi:10.3762/bjoc.21.33

• exposing fresh material to light. In 2016, König and co-workers exploited rod milling to develop a photomechanochemical approach for the riboflavin tetraacetate (RFTA)-catalyzed photocatalytic oxidation of alcohols to the corresponding carbonyl compounds upon irradiation with five LEDs (λ = 455 nm) [69

• oxidation of alcohols. The photos in Scheme 6 were reproduced from [69] (© 2016 M. Obst et al., published by Beilstein-Institut, distributed under the terms of the Creative Commons Attribution 4.0 International License, https://creativecommons.org/licenses/by/4.0). Photomechanochemical oxidation of 1,2

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

• the extremes of SN1 and SN2 pathway by employing the effect of counter ions, showing close resemblance with the SNi mechanism [41], conforming to the famous Winstein’s ion-pair theory [42] and draws analogy with chlorination of alcohols by thionyl chloride [43]. Incorporating the role of counter ion

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

• organoboron substrates 31, including -B(OH)2, -Bpin, -BF3K, and -Bneo (neopentyl borate) derivatives noted as “-[B]” in Scheme 11, to produce aliphatic alcohols and phenols 32 with moderate to excellent yields. The versatility of this method is highlighted by the broad substrate scope of more than 50 examples

• , which includes various aryl- and alkylboronates, showcasing its applicability across a range of chemical transformations. For example, phenylboronic acids with diverse substitution patterns (such as electron-donating and electron-withdrawing groups) were smoothly converted to the corresponding alcohols

• alcohols 32. Notably, this protocol is both energy-efficient and operationally simple, with the reaction being carried out under air in ethanol, a low-toxicity solvent. Moreover, the scalability of the reaction was demonstrated with larger-scale experiments (up to 5 mmol), achieving excellent yields and

Dioxazolones as electrophilic amide sources in copper-catalyzed and -mediated transformations

• Seungmin Lee,
• Minsuk Kim,
• Hyewon Han and
• Jongwoo Son

Beilstein J. Org. Chem. 2025, 21, 200–216, doi:10.3762/bjoc.21.12

• conventionally challenging functionalizations, such as N- or O-arylations using aryl halides [29][30][31][32][33][34][35][36][37][38] or arylboronic acids [39][40][41][42], hydrofunctionalizations of unsaturated motifs [25][43][44][45][46][47][48][49][50][51][52][53][54][55][56], the oxidation of alcohols [57

Cu(OTf)₂-catalyzed multicomponent reactions

• Sara Colombo,
• Camilla Loro,
• Egle M. Beccalli,
• Gianluigi Broggini and
• Marta Papis

Beilstein J. Org. Chem. 2025, 21, 122–145, doi:10.3762/bjoc.21.7

• cascade reaction for the preparation of α-alkoxy-N-alkyltriazoles 44 that was developed starting from aliphatic aldehydes, alcohols, TMSN3 as azide source and alkynes (Scheme 33) [52]. The reaction occurs under mild conditions in acetonitrile at room temperature but is inhibited when using aromatic

• aldehydes and phenols. The mechanism involves the reaction of the azide with the hemiacetal XLII generated in situ from the aldehydes and alcohols, followed by coupling with the alkynes to form the triazole ring. Both, copper triflate and copper metal are essential for the success of the reaction. On the

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

• prochiral 2-aryloxyisophthalaldehydes 57a,b with a range of aliphatic and aromatic alcohols 58a–g, as well as heteroaromatic amines 60 (Scheme 19). Chiral diaryl ethers of this type received increased attention lately. Biju, Gao, Zhang, and Zeng groups all reported high degrees of yields and

• enantioselectivity during the nucleophilic addition, and the subsequent aromatization completes central-to-axial chirality conversion delivering products 68. Dynamic kinetic resolution of naphthylindoles 69 was performed by reaction with bulky electrophiles such as azodicarboxylates 70 or o-hydroxybenzyl alcohols 72

• of products in low to satisfactory yields, but having high enantiomeric purities. An organocatalytic asymmetric (3 + 2) cyclization of 3-arylindoles 154 with either achiral 155 or racemic 157 propargylic alcohols was reported by Wu et al. (Scheme 46) [74]. Utilizing CPA C37 with 3-arylindoles 154 and

Non-covalent organocatalyzed enantioselective cyclization reactions of α,β-unsaturated imines

• Sergio Torres-Oya and
• Mercedes Zurro

Beilstein J. Org. Chem. 2024, 20, 3221–3255, doi:10.3762/bjoc.20.268

• dihydropyridinones 49 and 51 in moderate to good yields (45–76%), excellent diastereoselectivities and high enantioselectivities (85–94% ee) (Scheme 18). The reaction was also compatible with 1,1-dialkyl-substituted 3-amidoallylic alcohols 50 as precursors of α,β-unsaturated N–H ketimines; in this case the chiral

Synthesis of 2H-azirine-2,2-dicarboxylic acids and their derivatives

• Anastasiya V. Agafonova,
• Mikhail S. Novikov and
• Alexander F. Khlebnikov

Beilstein J. Org. Chem. 2024, 20, 3191–3197, doi:10.3762/bjoc.20.264

• a 4 mmol scale gave dimethyl ester 11a in 99% yield. Unexpectedly, the reaction of branched alcohols with diacyl chloride 2a failed. For example, the reaction with benzyl alcohol resulted in the formation of an overly complex mixture of products. Adding bases to trap HCl did not improve the

• reaction of more branched alcohols failed. Such esters could be prepared from the dicarboxylic acids using traditional activation or OH-insertion reaction of carbenes formed by irradiation of the appropriate diazo compound. Approaches to 2H-azirine-2,2-dicarboxylic acid derivatives. Synthesis of 2H-azirine