Visible-light-driven NHC and organophotoredox dual catalysis for the synthesis of carbonyl compounds

• Vasudevan Dhayalan

Beilstein J. Org. Chem. 2025, 21, 2584–2603, doi:10.3762/bjoc.21.200

• cross-coupling between the C-centered and N-centered radicals. These methods are expected to open new avenues for visible-light- and NHC/4CzIPN-catalyzed carbon–heteroatom bond-forming processes (Scheme 1) [51]. In 2021, Studer et al. developed a novel method for the 1,3-difunctionalization of

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

• for the construction of carbon–carbon and carbon–heteroatom bonds. Unlike many ionic reactions, radical reactions are often functional group tolerant and carried out under mild, neutral conditions, avoiding harsh acidic or basic conditions that can promote epimerization or decomposition of the product

• transferred to the radical. Important processes of this kind are hydrogen atom transfer (HAT) and halogen atom abstraction. An intramolecular group transfer reaction can result in the net migration of a functional group. Addition of a radical to a π-bond (carbon–carbon or carbon–heteroatom) is another common

Pathway economy in cyclization of 1,n-enynes

• Hezhen Han,
• Wenjie Mao,
• Bin Lin,
• Maosheng Cheng,
• Lu Yang and
• Yongxiang Liu

Beilstein J. Org. Chem. 2025, 21, 2260–2282, doi:10.3762/bjoc.21.173

• under gold(I) catalysis through a substituent-controlled strategy (Scheme 8) [15]. Substrates with heteroaryl substituents underwent 6-endo-dig cyclization via gold-heteroatom coordination, furnishing the lactone-fused pyran scaffold 34 (Scheme 8, path a). Substrates with aryl substituents at the

Photochemical reduction of acylimidazolium salts

• Michael Jakob,
• Nick Bechler,
• Hassan Abdelwahab,
• Fabian Weber,
• Janos Wasternack,
• Leonardo Kleebauer,
• Jan P. Götze and
• Matthew N. Hopkinson

Beilstein J. Org. Chem. 2025, 21, 1973–1983, doi:10.3762/bjoc.21.153

• employed including carboxylic acids [37], xanthates [38], electron-rich toluene or heteroatom-substituted species [39][40][41][42], organoboron compounds [43][44] and organosilanes [43][45]. Moreover, three-component radical relay processes employing styrene derivatives have also been widely studied. In

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

• ]arenes displayed a distinctive 1,3-alternate conformation, notably differing from the typical cone conformation of the conventional calix[4]arenes. Moreover, unlike previously documented examples, the inherent chirality of these products arises from the difference of just one heteroatom (O and NH) in the

Transition-state aromaticity and its relationship with reactivity in pericyclic reactions

• Israel Fernández

Beilstein J. Org. Chem. 2025, 21, 1613–1626, doi:10.3762/bjoc.21.125

• the lower barriers computed for the Hopf cyclizations of ene–ene–ynes E=CH–CH=CH–C≡CH where the terminal CH2 group was replaced by a heteroatom (E = NH or O). Figure 8 shows the corresponding ASDs for the parent cyclization (E = CH2) and the analogous process involving the imine system (E = NH). In

Facile synthesis of hydantoin/1,2,4-oxadiazoline spiro-compounds via 1,3-dipolar cycloaddition of nitrile oxides to 5-iminohydantoins

• Juliana V. Petrova,
• Varvara T. Tkachenko,
• Victor A. Tafeenko,
• Anna S. Pestretsova,
• Vadim S. Pokrovsky,
• Maxim E. Kukushkin and
• Elena K. Beloglazkina

Beilstein J. Org. Chem. 2025, 21, 1552–1560, doi:10.3762/bjoc.21.118

• form two new carbon–heteroatom bonds in a 1,2,4-oxadiazoline ring through both variants of orbital overlap. It should be noted that, in this case, NMR spectroscopy is not applicable to assign the product structure due to the presence of only quaternary carbon atoms in the tetrasubstituted 1,2,4

• known that nitrile oxides are capable of reacting with various multiple carbon–heteroatom bonds [28]. In contrast to the products of nitrile oxide cycloaddition to imino groups, 1,4,2-oxathiazoles, formed by addition to C=S bonds, are unstable and undergo decomposition into isothiocyanate and a carbonyl

• in the formation of two new carbon–heteroatom bonds and the formation of a five-membered ring. Thus, the aryl attached to the nitrogen atom from the dipolarophile fragment is brought closer to the substituent from the C-end of the dipole. This proximity in the presence of ortho-substituents in the

Azide–alkyne cycloaddition (click) reaction in biomass-derived solvent Cyrene^TM under one-pot conditions

• Zoltán Medgyesi and
• László T. Mika

Beilstein J. Org. Chem. 2025, 21, 1544–1551, doi:10.3762/bjoc.21.117

• and atom-economical strategies for efficiently assembling new carbon–carbon [1][2][3] and carbon–heteroatom [4][5][6] bonds. Thus, it has become the most attractive and facile methodology for creating various complex organic molecular structures from the laboratory to the industrial scale. Among these

• successfully introduced into homogeneous [26][27][28][29] and heterogeneous [30][31] carbon–carbon and carbon–heteroatom bond-forming protocols. Although its reactive carbonyl group could limit its application when a strong base (aldol condensation [29]) or amines (potential Schiff-base formation) are present

Copper catalysis: a constantly evolving field

• Elena Fernández and
• Jaesook Yun

Beilstein J. Org. Chem. 2025, 21, 1477–1479, doi:10.3762/bjoc.21.109

• , decarboxylative functionalizations, and Chan–Lam coupling reactions. In doing so, the authors point out the combination of transition-metal catalysis and electrochemistry as an efficient, sustainable method for the oftentimes challenging formation of C–C and C–heteroatom bonds in complex molecules. Another Review

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

• helical architectures, have attracted considerable attention due to their intrinsic chirality and tunable optoelectronic properties. Among them, nitrogen-doped helicenes (azahelicenes) and their heteroatom-co-doped counterparts – such as B/N-, O/N-, S/N-, and Se/N-doped helicenes – have emerged as highly

• emitters. Boron–nitrogen co-doping strategies, in particular, have facilitated the development of materials with ultra-narrowband emissions, near-unity photoluminescence quantum yields, and electroluminescence dissymmetry factors (|gEL|) exceeding 10−3. Likewise, heteroatom co-doping with oxygen, sulfur

• systems – has granted access to increasingly complex helicene frameworks with well-defined chirality. This review systematically summarizes recent advancements in the synthesis, structural engineering, and chiroptical performance of nitrogen-doped helicenes and their heteroatom-doped derivatives

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

• epoxides and heteroatom-stabilised carbocations generated from alkenes (Scheme 10). In 1992, Arjona and co-workers examined the synthesis of 4,7-dioxatricyclo[3.2.1.03,6]octane derivatives 45 via intramolecular cyclisation of the corresponding hydroxyalkene precursors 44 using arylsulphenyl and arylselenyl

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

• C–C or C–heteroatom bonds. The incorporation of HAT strategies into the functionalization of C–H bonds represents a significant advancement in synthetic organic chemistry for their high atom economy and step economy. HAT reagents (HR), including alkoxyl, acyloxyl, halogen radicals, and amidyl

Recent advances and future challenges in the bottom-up synthesis of azulene-embedded nanographenes

• Bartłomiej Pigulski

Beilstein J. Org. Chem. 2025, 21, 1272–1305, doi:10.3762/bjoc.21.99

• scaffolds of this type. Given the rapid progress in this field, with nearly half of the cited works published since 2020, this review focuses primarily on purely hydrocarbon structures, with less emphasis on heteroatom-containing molecules. Typically, only the final synthetic steps leading to the fused

• gap 1.07 eV) which is impressive for such small π-scaffold. Formation of carbon–heteroatom bonds: Although the primary focus of this review is the synthesis of all-carbon azulene-embedded nanographenes, some carbon–heteroatom fusion reactions are also worth mentioning. In general, azulene-fused

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

• heteroatom for the synthesis of functionalized oxindoles was also reported in 2013 [3]. In this study, DBU was employed as a ligand and TBHP as an oxidant. A series of ethers, including 1,2-dimethoxyethane, THF, 1,4-dioxane, tetrahydro-2H-pyran, 2,3-dihydrobenzofuran, tetrahydro-2H-thiopyran, and N

Enhancing chemical synthesis planning: automated quantum mechanics-based regioselectivity prediction for C–H activation with directing groups

• Julius Seumer,
• Nicolai Ree and
• Jan H. Jensen

Beilstein J. Org. Chem. 2025, 21, 1171–1182, doi:10.3762/bjoc.21.94

• activation, transforming these inert bonds into reactive carbon–transition metal (C–M) bonds. Subsequent transformations of these complexes enable the formation of an array of new functional groups, such as carbon–carbon and carbon–heteroatom bonds, underpinning a plethora of synthetic applications

• in Figure 1. Using this approximation the generation and optimization of structures simplifies greatly. In an automatized workflow, all unique and possible combinations of C–H bonds and ortho-directing groups (heteroatom with lone pair) in the substrate are found following this procedure: 1. All

• combinations of C–H bonds from sp2-hybridized C atoms and directing groups (heteroatom with lone pair) in the substrate, which are between two and five bonds apart from each other, are detected with SMART patterns. These patterns are general enough to cover all directing groups that were encountered in the

Supramolecular assembly of hypervalent iodine macrocycles and alkali metals

• Krishna Pandey,
• Lucas X. Orton,
• Grayson Venus,
• Waseem A. Hussain,
• Toby Woods,
• Lichang Wang and
• Kyle N. Plunkett

Beilstein J. Org. Chem. 2025, 21, 1095–1103, doi:10.3762/bjoc.21.87

• heteroatoms at axial positions resulting in a three-center four-electron bond [13][14]. In this unique “T” configuration, the bond length between iodine and one of the heteroatoms is influenced by the bond distance of the other heteroatom and is responsible for the stabilization of the hypervalent iodine

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

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

• photooxidant or photoreductant in the presence of a suitable electron donor or acceptor [18], and these properties have been exploited in procedures for the formation of both C–C and C–heteroatom bonds [18][19]. Our research groups recently focused on the application of CDs in light-mediated organic synthesis

Synthesis and photoinduced switching properties of C₇-heteroatom containing push–pull norbornadiene derivatives

• Daniel Krappmann and
• Andreas Hirsch

Beilstein J. Org. Chem. 2025, 21, 807–816, doi:10.3762/bjoc.21.64

• Daniel Krappmann Andreas Hirsch Department Chemistry and Pharmacy, Friedrich-Alexander-Universität Erlangen-Nürnberg, Nikolaus-Fiebiger Straße 10, 91058 Erlangen, Germany 10.3762/bjoc.21.64 Abstract We report the synthesis and characterization of heteroatom-incorporated norbornadiene (NBD

• little attention in the literature, with investigations largely limited to forward conversions [35]. Here, we present 2,3-heteroatom-incorporated NBD derivatives and compare their properties with those of previously published isocyclic derivatives. By utilizing push–pull functionalization and

• heteroatom. As an additional significant signal, the singlet at 1.34 ppm corresponding to the nine protons of the Boc group can be found. After 5 minutes of irradiation, the majority of N-NBD2 is consumed, finished after 15 minutes with the complete generation of a newly formed species. The spectral features

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

• electrosynthesis as a green, precise, and low-cost method to prepare phosphorous structures. Keywords: electrosynthesis; green synthesis; organophosphorus compounds; P–C bond formation; P–heteroatom bond formation; Introduction The electrochemical synthesis is a valuable and beneficial method for the preparation

• organophosphorus compounds, in which phosphorus is attached to carbon or heteroatom centers. In this article, we describe recent advances in electrochemical green methods for the synthesis of various organophosphorus compounds through the formation of phosphorus–carbon, phosphorus–nitrogen, phosphorus–oxygen

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

• macrocycle [74][75]. 2 Ethers We now turn our attention from alkanes to what is arguably the simplest heteroatom-containing functional group: the ether. The presence of oxygen within a carbon chain offers several new opportunities for engagement by an introduced fluorine atom. First, we will consider what

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

• significance of this transformation lies in its unique ability to efficiently create a stereogenic center while forming new carbon–carbon or carbon–heteroatom bonds (e.g., C–N, C–O, and C–S) with excellent selectivities. The field of metal-catalyzed allylic substitution has evolved significantly since its

Synthesis of N-acetyl diazocine derivatives via cross-coupling reaction

• Thomas Brandt,
• Pascal Lentes,
• Jeremy Rudtke,
• Michael Hösgen,
• Christian Näther and
• Rainer Herges

Beilstein J. Org. Chem. 2025, 21, 490–499, doi:10.3762/bjoc.21.36

• provided the corresponding amino-substituted N-acetyl diazocine 21 (Scheme 1). Another option for carbon–heteroatom bond formation reactions are copper-catalyzed Ullmann-type reactions, which have already been applied to the parent diazocine [36][37]. The attempted synthesis of azide-functionalized N

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

• organometallic catalysis [15], enzymatic catalysis [16], aminocatalysis [17][18][19], and hydrogen-bonding catalysis [20][21][22]. The Michael addition reaction is a versatile synthetic methodology that allows the formation of new carbon–carbon and carbon–heteroatom bonds through the coupling of electron-poor

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

• light and promote mass transfer. As understanding of the methodology advances, the development of more complex synthetic strategies, including C–H, C–C, and C–heteroatom-bond formation, is expected [79]. Moreover, we anticipate that the difference in photophysical properties between organic molecules in