Catalytic enantioselective synthesis of selenium-containing atropisomers via C–Se bond formations

• Qi-Sen Gao,
• Zheng-Wei Wei and
• Zhi-Min Chen

Beilstein J. Org. Chem. 2025, 21, 2447–2455, doi:10.3762/bjoc.21.186

• enantioselective synthesis of atropisomers, and significant progress has been made in recent years. However, selenium-containing atropisomers have long remained underexplored as synthetic targets, and only in recent years have they begun to attract increasing attention from the community. Recently, several

• currently lacking. This review aims to provide an overview of recent developments in the catalytic enantioselective synthesis of selenium-containing atropisomers via C–Se bond formation. We hope this review will serve as a valuable reference for researchers interested in further exploring this area

• VQM intermediate Int 9 and benzenesulfonic acid. Finally, benzenesulfonic acid further reacts with the VQM intermediate to afford product 9, concomitant with regeneration of the catalyst. This protocol provides a promising approach for the enantioselective synthesis of axially chiral styrenes

Transformation of the cyclohexane ring to the cyclopentane fragment of biologically active compounds

• Natalya Akhmetdinova,
• Ilgiz Biktagirov and
• Liliya Kh. Faizullina

Beilstein J. Org. Chem. 2025, 21, 2416–2446, doi:10.3762/bjoc.21.185

• obtaining medically interesting dactylicapnosine-like analogues for detailed study of their biological activity. Matoba et al. [45] reported the first enantioselective synthesis of the hasubanane alkaloid (−)-metaphanine (70) and the norhasubanane alkaloid (+)-stephadiamine (71) using a cyclohexane ring

• with 52% yield (Scheme 14). The authors [47] provided convincing evidence that the acyloin ring contraction is stereospecific, by replacing the benzil ᴅ-glucose in compound 76 at the C5 atom with an achiral prenyl group. In [49], Zhang and co-workers carried out the first enantioselective synthesis of

• . Next, ion 88 reacted with the isopropenyl group, forming intermediate 89, which was then converted into the desired 2,8-oxymethano-bridged diquinane 90 in 90% yield (Scheme 16). In the enantioselective synthesis of sesquiterpenoids (+)-cuparene (91) and (+)-tochuinyl acetate (92), Xie and co-workers

Halogenated butyrolactones from the biomass-derived synthon levoglucosenone

• Johannes Puschnig,
• Martyn Jevric and
• Ben W. Greatrex

Beilstein J. Org. Chem. 2025, 21, 2297–2301, doi:10.3762/bjoc.21.175

• chiral halogenated lactones, which could be useful in the enantioselective synthesis of valuable drug precursors. The syntheses feature the use of readily available and cheap starting materials, and we have also demonstrated some of these transformations on a gram scale. Halogen-containing butyrolactone

Enantioselective radical chemistry: a bright future ahead

• Anna C. Renner,
• Sagar S. Thorat,
• Hariharaputhiran Subramanian and
• Mukund P. Sibi

Beilstein J. Org. Chem. 2025, 21, 2283–2296, doi:10.3762/bjoc.21.174

• transformations is also discussed. Keywords: chiral Lewis acid; electrochemistry; enantioselective radical reaction; organocatalysis; photoenzymatic catalysis; photoredox; Introduction Asymmetric catalysis plays an integral role in the enantioselective synthesis of organic compounds. A wide variety of

Further elaboration of the stereodivergent approach to chaetominine-type alkaloids: synthesis of the reported structures of aspera chaetominines A and B and revised structure of aspera chaetominine B

• Jin-Fang Lü,
• Jiang-Feng Wu,
• Jian-Liang Ye and
• Pei-Qiang Huang

Beilstein J. Org. Chem. 2025, 21, 2072–2081, doi:10.3762/bjoc.21.162

• alkaloids and antipodes. Enantioselective synthesis of the proposed structure of aspera chaetominine A. Enantioselective syntheses of both the proposed and revised structures of aspera chaetominine B. Supporting Information Supporting Information File 4: General methods and materials, experimental

Enantioselective desymmetrization strategy of prochiral 1,3-diols in natural product synthesis

• Lihua Wei,
• Rui Yang,
• Zhifeng Shi and
• Zhiqiang Ma

Beilstein J. Org. Chem. 2025, 21, 1932–1963, doi:10.3762/bjoc.21.151

• , thus completing the enantioselective synthesis of (−)-heliannuol D and (+)-heliannuol A (Scheme 6) [37]. The monoester (S)-11 was isolated in 87% yield with >99% ee. A subsequent 17-step sequence provided epoxides 38 and 39. Treatment of the mixture of 38 and 39 with 5% NaOH aqueous solution resulted

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

• , including the asymmetric [2 + 2 + 2] cycloaddition of aryl-substituted polyynes and hydroarylation of alkynes [18][19]. In contrast, the application of asymmetric organocatalysis for enantioselective synthesis of chiral helicenes remains relatively underdeveloped compared to transition metal-catalyzed

• enantioselective synthesis of planarly chiral macrocycles through a dynamic kinetic resolution approach [15]. Despite bearing an amino group on the phenyl ring, the configuration of the macrocyclic paracyclophane 32 was found to be unstable at room temperature. Consequently, by employing a CPA-catalyzed asymmetric

• asymmetric synthesis of planarly chiral macrocyclic paracyclophane 47 from the corresponding hydroxy-substituted carboxylic acid substrate 46. Notably, the authors also demonstrated the application of this method in the enantioselective synthesis of axially chiral C–N and N–N atropisomers, highlighting the

Advances in nitrogen-containing helicenes: synthesis, chiroptical properties, and optoelectronic applications

• Meng Qiu,
• Jing Du,
• Nai-Te Yao,
• Xin-Yue Wang and
• Han-Yuan Gong

Beilstein J. Org. Chem. 2025, 21, 1422–1453, doi:10.3762/bjoc.21.106

• responses. Concurrently, Tanaka’s group achieved the enantioselective synthesis of aza[6]- and aza[7]helicene-like molecules via Rh(I)/chiral bisphosphine-catalyzed [2 + 2 + 2] cycloaddition [80]. The resulting S-shaped double aza[6]helicene-like compound 66 displayed high enantiomeric excess (up to 89% ee

• , the team achieved the enantioselective synthesis of heterodehydrospiroenes on a gram scale using chiral vanadium(V) complexes – marking a significant advancement in asymmetric electrochemical catalysis. In a complementary study that same year, they reported a two-step electrochemical synthesis of a

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

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

• require dineopentyl aziridine-2,2-dicarboxylates to realize high enantioselectivity, while the synthesis of the chiral ligand N,N'-dioxide requires multiple steps. Herein, we present a convenient highly diastereo- and enantioselective synthesis of dialkyl 2,5-diaryl-1-sulfonyloxazolidine-2,2

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

• the benzylic alcohol, a 1,2-Grignard addition and an AcOH-interrupted Nazarov cyclization. Keywords: enantioselective synthesis; interrupted Nazarov cyclization; khayanolide-type limonoids; tetracyclic framework; Introduction Limonoids, a class of tetranortriterpenoids derived biosynthetically from

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

• hydrocyanation of hydrazones, catalyzed by a calcium–BINOL phosphate complex, has been studied for the first time both experimentally and computationally with DFT methods. A full catalytic cycle for the enantioselective synthesis of α-hydrazinonitriles is proposed based on insights gained from DFT calculations

Copper-catalyzed domino cyclization of anilines and cyclobutanone oxime: a scalable and versatile route to spirotetrahydroquinoline derivatives

• Qingqing Jiang,
• Xinyi Lei,
• Pan Gao and
• Yu Yuan

Beilstein J. Org. Chem. 2025, 21, 749–754, doi:10.3762/bjoc.21.58

• azetidinones, enabling the efficient and enantioselective synthesis of tetrahydroquinoline-fused azetidines with three contiguous stereocenters in a single step [23]. Later, Tanaka, Nagashima, and their co-workers established a chemo-, regio-, and diastereoselective dearomative transformation of quinolines

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

• products. The high stereochemical selectivity of both SN2 and SN2' pathways enabled the efficient construction of complex molecular frameworks. Notably, this approach facilitated the enantioselective synthesis of three ant pheromones: (+)-lasiol, (+)-13-norfaranal, and (+)-faranal. The synthesis of

• alkynes in a chemo-, regio-, and enantioselective manner represents a recent advance in copper hydride chemistry. Along these lines, in 2024, Su and co-workers developed a strategy for the copper-catalyzed regio- and enantioselective synthesis of secondary homoallylboron compounds by assembling four

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

• yields [27]. These reactions have been utilized in the enantioselective synthesis of aryl sulfoxides through the arylation of sulfonate anions in the presence of palladium catalysts [28][29]. They have also been used in the synthesis of the neuraminidase inhibitor (−)-oseltamivir [30] and the

• enantiocontrol [34][35][36][37][38][39]. In our studies on the organocatalytic enantioselective synthesis of 1,5-ketoaldehydes [40], we found that the prolinol derivative A is an outstanding catalyst for the enantioselective preparation of these adducts (Scheme 2). We are currently investigating whether this

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

• area of medicinal chemistry [93][94][95][96][97]. In 2018, Buchwald and co-workers unveiled the enantioselective synthesis of benzylic amines through the asymmetric Markovnikov hydroamidation of alkenes utilizing diphenylsilane in copper catalysis under mild reaction conditions [98]. Dioxazolones, as

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

• -dihydroquinazolin-4(1H)-one derivatives 26. Synthesis of polysubstituted pyrroles 27. Enantioselective synthesis of polysubstituted pyrrolidines 30 directed by the copper complex 29. Synthesis of 4,5-dihydropyrazoles 31. Synthesis of 2 arylisoindolinones 32. Synthesis of imidazo[1,2-a]pyridines 33. Synthesis of

Access to optically active tetrafluoroethylenated amines based on [1,3]-proton shift reaction

• Yuta Kabumoto,
• Eiichiro Yoshimoto,
• Bing Xiaohuan,
• Masato Morita,
• Motohiro Yasui,
• Shigeyuki Yamada and
• Tsutomu Konno

Beilstein J. Org. Chem. 2024, 20, 2776–2783, doi:10.3762/bjoc.20.233

• reports on the preparation of chiral molecules possessing a tetrafluoroethylene unit on an asymmetric carbon center in a high optical purity, and to the best of our knowledge, only the following have been published so far (Scheme 1). As a highly enantioselective synthesis, there has been a pioneering work

5th International Symposium on Synthesis and Catalysis (ISySyCat2023)

• Anthony J. Burke and
• Elisabete P. Carreiro

Beilstein J. Org. Chem. 2024, 20, 2704–2707, doi:10.3762/bjoc.20.227

• organocatalyst for the gram-scale enantioselective synthesis of (S)-baclofen”, an interesting approach to recycling the very useful cinchona squaramide organocatalysts was described. This approach involved functionalization of the organocatalyst with a lipophilic linker (octadecyl side chains), resulting in a

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

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

• concerted SN2-key intermediate 60 must be at least 18.9 kcal/mol more favoured than a separated imine–chloride ion pair 61 attacked by the free allylsilane (Figure 3). Altogether, the developed methodology can be formally viewed as a useful tool for the enantioselective synthesis of chiral α-carboxyl-2,3

Primary amine-catalyzed enantioselective 1,4-Michael addition reaction of pyrazolin-5-ones to α,β-unsaturated ketones

• Pooja Goyal,
• Akhil K. Dubey,
• Raghunath Chowdhury and
• Amey Wadawale

Beilstein J. Org. Chem. 2024, 20, 1518–1526, doi:10.3762/bjoc.20.136

• (Scheme 2) were obtained in good to excellent yields (71–97%) and enantioselectivities (83.5–98% ee). Molecules containing two or more biologically relevant heterocycle motifs are receiving attention in drug discovery research [31][32][33]. The enantioselective synthesis of such hybrid molecules is

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

• -β-lactone core 73 (Scheme 21). An expedient use of the Cannizzaro reaction was exemplified in the noteworthy enantioselective synthesis towards the indole alkaloids 16-epivellosimine, (+)-polyneuridine, and (+)-macusine A as reported by Cook and coworkers [89]. This was effectively worked out from ᴅ

Enantioselective synthesis of β-aryl-γ-lactam derivatives via Heck–Matsuda desymmetrization of N-protected 2,5-dihydro-1H-pyrroles

• Arnaldo G. de Oliveira Jr.,
• Martí F. Wang,
• Rafaela C. Carmona,
• Danilo M. Lustosa,
• Sergei A. Gorbatov and
• Carlos R. D. Correia

Beilstein J. Org. Chem. 2024, 20, 940–949, doi:10.3762/bjoc.20.84

Chiral phosphoric acid-catalyzed transfer hydrogenation of 3,3-difluoro-3H-indoles

• Yumei Wang,
• Guangzhu Wang,
• Yanping Zhu and
• Kaiwu Dong

Beilstein J. Org. Chem. 2024, 20, 205–211, doi:10.3762/bjoc.20.20

• isostere of polar functional groups [5][6]. Chiral indoline is an important member of the class of nitrogen-containing heterocyclic compounds that often exhibits various pharmaceutical activities and exists in many natural products [7][8]. The enantioselective synthesis of chiral indolines has received