Chiral phosphoric acid-catalyzed asymmetric synthesis of helically chiral, planarly chiral and inherently chiral molecules

• Wei Liu and
• Xiaoyu Yang

Beilstein J. Org. Chem. 2025, 21, 1864–1889, doi:10.3762/bjoc.21.145

• synthesis of planarly chiral macrocycles via CPA-catalyzed coupling of carboxylic acids with alcohols via ynamide mediation. Kinetic resolution of substituted amido[2.2]paracyclophanes via CPA-catalyzed asymmetric electrophilic amination. Enantioselective synthesis of inherently chiral calix[4]arenes via

Photoswitches beyond azobenzene: a beginner’s guide

• Michela Marcon,
• Christoph Haag and
• Burkhard König

Beilstein J. Org. Chem. 2025, 21, 1808–1853, doi:10.3762/bjoc.21.143

Synthesis of chiral cyclohexane-linked bisimidazolines

• Changmeng Xi,
• Qingshan Sun and
• Jiaxi Xu

Beilstein J. Org. Chem. 2025, 21, 1786–1790, doi:10.3762/bjoc.21.140

• alcohols and utilized in different metal-catalyzed asymmetric organic reactions [1][2][3][4][5][6][7][8][9]. In comparison with bisoxazoline ligands, relatively less attention has been paid to bisimidazoline ligands [10][11][12][13][14][15]. Some well investigated bisimidazoline ligands are pyridine-linked

• vicinal amino alcohols as starting materials in their synthesis. However, it is difficult to tune the electronic effects of cHBOX ligands. Chiral cyclohexane-1,2-linked bisimidazolines possess similar structural features as cHBOX ligands and their electronic effect can be tuned by the introduction of

Preparation of a furfural-derived enantioenriched vinyloxazoline building block and exploring its reactivity

• Madara Darzina,
• Anna Lielpetere and
• Aigars Jirgensons

Beilstein J. Org. Chem. 2025, 21, 1737–1741, doi:10.3762/bjoc.21.136

• amino alcohols derived from furfural and ʟ- or ᴅ-valinol were subjected to Torii-type ester electrosynthesis to obtain the corresponding unsaturated esters. These served as key intermediates to prepare (S)- and (R)-enantioenriched unsaturated amides by N-Alloc deprotection which induced concomitant

• trans-isomer of amide 5. Results and Discussion The protected furfuryl amino alcohols S-2d and R-2d were prepared by reductive amination of furfural (1) with ʟ- and ᴅ-valinol followed by N-protection with Alloc-Cl (Scheme 2). The amino alcohols S-2d and R-2d were then subjected to electrochemical

• competent substrate for the aza-Diels–Alder reaction in with TsNCO to give oxazolo[3,2-c]pyrimidine derivative 7 as a single diastereomer. Proposed approach for the preparation of vinyloxazoline 6. Synthesis of furfuryl amino alcohols S-2d and R-2d and their electrochemical oxidation to esters S-3d and R-3d

Continuous-flow-enabled intensification in nitration processes: a review of technological developments and practical applications over the past decade

• Feng Zhou,
• Chuansong Duanmu,
• Yanxing Li,
• Jin Li,
• Haiqing Xu,
• Pan Wang and
• Kai Zhu

Beilstein J. Org. Chem. 2025, 21, 1678–1699, doi:10.3762/bjoc.21.132

• classifications necessitate tailored nitrating reagent selections, giving rise to fundamentally distinct mechanistic pathways. This reactivity is exemplified by the comparative kinetic profiles: N-nitration of amines and O-nitration of alcohols – facilitated by accessible lone electron pairs – exhibit markedly

General method for the synthesis of enaminones via photocatalysis

• Paula Pérez-Ramos,
• Raquel G. Soengas and
• Humberto Rodríguez-Solla

Beilstein J. Org. Chem. 2025, 21, 1535–1543, doi:10.3762/bjoc.21.116

• presence of amines and CuI as catalyst, as reported by Zhang and co-workers (Scheme 1B) [32]. On the other hand, Li et al. disclosed a silver-catalyzed amination of propargyl alcohols to afford enaminones (Scheme 1C) [33]. Although these new methods provide a wide variety of enaminones, there are

Calcium waste as a catalyst in the transesterification for demanding esters: scalability perspective

• Anton N. Potorochenko and
• Konstantin S. Rodygin

Beilstein J. Org. Chem. 2025, 21, 1520–1527, doi:10.3762/bjoc.21.114

• acetylene production, was investigated. The catalyst was obtained by calcination of calcium carbide slag at 600 °C (CS600) and characterized by XRD and FTIR analysis. The transesterification reactions were carried out with primary alcohols, producing fatty acid alkyl esters in 51–99% yields, depending on

• the alcohols’ nature and catalyst amount (1–10 wt %). The CS600 catalyst demonstrated efficiency in the transesterification of low-molecular-weight esters, medium-chain triglycerides (C9–C12), and lactones, resulting in the corresponding methyl esters in 66–99% yields in the presence of low catalyst

• applications [62][63][64][65][66][67][68][69][70][71]; however, the amount of slag is much higher than its actual consumption. In this work, the application of a catalyst derived from carbide slag in the transesterification of soybean oil with various alcohols (11 examples) was investigated. The carbide slag

High-pressure activation for the solvent- and catalyst-free syntheses of heterocycles, pharmaceuticals and esters

• Kelsey Plasse,
• Valerie Wright,
• Guoshu Xie,
• R. Bernadett Vlocskó,
• Alexander Lazarev and
• Béla Török

Beilstein J. Org. Chem. 2025, 21, 1374–1387, doi:10.3762/bjoc.21.102

• ; therefore, the use of pressure resulted in a more substantial improvement in the OH acylation reaction. HHP-assisted esterification of alcohols: synthesis of fragrances Esterification is one of the most common organic reactions and there are a multitude of processes available. However, most require some

•  4, entry 5) under pressure yielded quantitative product formation. The optimized conditions allowed the extension of the protocol and a selection of alcohols was investigated. The results are illustrated in Scheme 4. For comparison, results obtained from reactions at ambient pressure are given in

• pressurization even at 80 °C. However, the reaction rate with AcOH is still much improved under high pressure, as none of the alcohols formed any product under 1 bar pressure. Scale up of the HHP-assisted reactions The above protocols were carried out at a small scale (mg to g) and thus, an effort was made to

Oxetanes: formation, reactivity and total syntheses of natural products

• Peter Gabko,
• Martin Kalník and
• Maroš Bella

Beilstein J. Org. Chem. 2025, 21, 1324–1373, doi:10.3762/bjoc.21.101

• alcohols 13 and a binary Al/TBAB catalyst (Scheme 5) [40]. The reaction is carried out in toluene upon mild heating, providing the bicyclic products in high to excellent yields. Both electron-rich and electron-poor phenyls as well as aliphatic chains worked well, however, increased temperature and catalyst

• homoallylic alcohols 18/19 via metal hydride atom transfer/radical polar crossover (MHAT/RPC) method (Scheme 6) [41]. This mild and high-yielding protocol displays good functional group tolerance and has a broad substrate scope, even providing access to medicinally relevant spirooxetanes. The proposed MHAT

• with alcohol C–H functionalisation, thus creating a unique synthetic strategy towards oxetane formation that avoids tedious multistep substrate preparations (Scheme 7) [42]. It can be initiated from simple, unactivated primary or secondary alcohols, tolerates various functional groups such as acetals

Recent advances in amidyl radical-mediated photocatalytic direct intermolecular hydrogen atom transfer

• Hao-Sen Wang,
• Lin Li,
• Xin Chen,
• Jian-Li Wu,
• Kai Sun,
• Xiao-Lan Chen,
• Ling-Bo Qu and
• Bing Yu

Beilstein J. Org. Chem. 2025, 21, 1306–1323, doi:10.3762/bjoc.21.100

• cycloalkenes and alcohols. To eliminate the need for noble metal photocatalysts in the system, Duan’s group employed 2,4,5,6-tetra-9H-carbazol-9-yl-1,3-benzenedicarbonitrile (4CzIPN) as a metal-free photocatalyst (Scheme 3) [71]. This system initiated the formation of amidyl radical 20 from HRP-3 through a

Recent advances in oxidative radical difunctionalization of N-arylacrylamides enabled by carbon radical reagents

• Jiangfei Chen,
• Yi-Lin Qu,
• Ming Yuan,
• Xiang-Mei Wu,
• Heng-Pei Jiang,
• Ying Fu and
• Shengrong Guo

Beilstein J. Org. Chem. 2025, 21, 1207–1271, doi:10.3762/bjoc.21.98

• -/trifluoroalkylation reagents, α-carbonyl alkyl bromides/alcohols, alkyl halides, and alkyl carboxylic acids, have been successfully applied to this transformation to afford 3-substituted indolin-2-ones. In 2013, Li’s group reported a novel DTBP(di-tert-butyl peroxide)-mediated oxidative 1,2-alkylarylation of

• -free synthetic method for 3,3-disubstituted oxindoles via 1,2-alkylarylation of activated alkenes with alcohols [4]. N-Arylacrylamides and simple alcohols were employed as substrates, proceeding through an oxidative radical cyclization mechanism. The standard reaction conditions involved the use of an

• and alcohols. Substrates with different substituents, including both electron-donating and electron-withdrawing groups, provided satisfactory yields (7a–f). However, steric hindrance significantly influenced the outcome, as ortho-substituted substrates yielded lower amounts (7c). The study also

Selective monoformylation of naphthalene-fused propellanes for methylene-alternating copolymers

• Kenichi Kato,
• Tatsuki Hiroi,
• Seina Okada,
• Shunsuke Ohtani and
• Tomoki Ogoshi

Beilstein J. Org. Chem. 2025, 21, 1183–1191, doi:10.3762/bjoc.21.95

• moderate flexibility at the same time. Therefore, the monoformyl products are good precursors for soft materials which show molecular-size cavities and require desymmetrized building blocks. As a proof of concept, methylene-alternating copolymers were prepared by reduction to corresponding alcohols

• interactions between the naphthalene units. The monoformyl products are reduced to corresponding alcohols, which are then reacted under Friedel–Crafts conditions. Amorphous methylene-alternating copolymers are obtained without particular macrocyclic oligomers. Due to the 3D components, the linear copolymers

• -fused propellanes simply by reduction into the corresponding alcohols followed by acid-mediated Friedel–Crafts-type reactions (Figure 2a and Figure S201 in Supporting Information File 1) [67][68]. Reduction by NaBH4 proceeded well for both monoaldehydes [4.3.3]_CHO and [3.3.3]_CHO resulting in over 90

Synthetic approach to borrelidin fragments: focus on key intermediates

• Yudhi Dwi Kurniawan,
• Zetryana Puteri Tachrim,
• Teni Ernawati,
• Faris Hermawan,
• Ima Nurasiyah and
• Muhammad Alfin Sulmantara

Beilstein J. Org. Chem. 2025, 21, 1135–1160, doi:10.3762/bjoc.21.91

• alcohols, 34 and ent-34, after recrystallization from hot hexane (100% ee by chiral phase HPLC, yield not reported). These alcohols were then treated with triphenylphosphine and iodine in the presence of imidazole to yield the iodides 35 and ent-35 (Scheme 2). The iodide intermediates were subsequently

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