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

• –c) and electron-withdrawing (e.g., fluorine, chlorine, ester groups) (78d–f) substituents on bromodifluoroacetamides were well tolerated, yielding high reaction efficiency. Interestingly, the reaction was less sensitive to electronic effects on the aromatic ring, as yields remained high regardless

On the photoluminescence in triarylmethyl-centered mono-, di-, and multiradicals

• Daniel Straub,
• Markus Gross,
• Mona E. Arnold,
• Julia Zolg and
• Alexander J. C. Kuehne

Beilstein J. Org. Chem. 2025, 21, 964–998, doi:10.3762/bjoc.21.80

• electronic effects will cause the Cz-unit to twist out of conjugation almost completely with the TTM radical core plane, leading to marginal orbital overlap between the D0 and D1 states. The reason for this increase in fluorescence lifetime τ is not completely understood; however, if the emission involves a

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

• preferentially occupied the palladium coordination site. Sequential insertion of CO and aryne, followed by reductive elimination, culminated in acridone formation. This ligand-dependent mechanistic dichotomy underscores the critical interplay between aryne availability, steric modulation, and electronic effects

• influence of steric and electronic effects during the hydrometallation process, simultaneously achieving the synthesis of chiral α-quaternary carbon amino acid derivatives 26 and α-chiral β-amino acid derivatives 27. Using a copper catalyst, the chiral α-quaternary carbon amino acid derivatives 26 were

Substituent effects in N-acetylated phenylazopyrazole photoswitches

• Radek Tovtik,
• Dennis Marzin,
• Pia Weigel,
• Stefano Crespi and
• Nadja A. Simeth

Beilstein J. Org. Chem. 2025, 21, 830–838, doi:10.3762/bjoc.21.66

• medicine. Despite their potential, their structural diversity is still limited and a larger pool of substitution patterns remains to be systematically investigated. This is paramount as electronic effects play a crucial role in the behavior of photoswitches and a deeper understanding enables their

• straightforward development for specific applications. In this work, we synthesized novel N-acylpyrazole-based photoswitches and conducted a comparative study with 33 phenylazopyrazoles, comparing their photoswitching properties and the impact of electronic effects. Using UV–vis and NMR spectroscopy, we

• investigated in detail and allowed to correlate thermal relaxation rates and steric or electronic effects as well as mechanistic peculiarities, which has been in the spotlight recently for different classes of azobenzenes [34]. Despite these studies, the variety of substitution patterns in PAPs is limited

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

• meta or ortho positions, which may be due to steric and electronic effects. The reaction proceeded via a radical process by forming Ph2P(O)H (Scheme 16). The reaction failed to give the corresponding product when using TEMPO in the reaction mixture. Zhang and co-workers [61] reported an electrochemical

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

• formed 17g in good yield and diastereoselectivity with decreased enantioselectivity, likely due to electronic effects. 6-Bromo- and 7-chloro-substituted substrates also provided 17h and 17i in good yields with moderate to good stereoselectivities. Next, Cbz-protected imine 7j was employed in the present

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

• 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

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

Phenylseleno trifluoromethoxylation of alkenes

• Clément Delobel,
• Armen Panossian,
• Gilles Hanquet,
• Frédéric R. Leroux,
• Fabien Toulgoat and
• Thierry Billard

Beilstein J. Org. Chem. 2024, 20, 2434–2441, doi:10.3762/bjoc.20.207

• ], electronic effects [17][18], and conformation [19][20][21]. Some trifluoromethoxylated molecules can be used as drugs in the treatment of various pathologies (Figure 1) [22][23][24][25][26][27][28][29]. On the other hand, despite its toxicity at higher doses, selenium is also an essential trace element in

Catalysing (organo-)catalysis: Trends in the application of machine learning to enantioselective organocatalysis

• Stefan P. Schmid,
• Leon Schlosser,
• Frank Glorius and
• Kjell Jorner

Beilstein J. Org. Chem. 2024, 20, 2280–2304, doi:10.3762/bjoc.20.196

• effects, the representation of electronic effects has also been further developed. Milo et al. [58] introduced the intensity and frequency of manually selected molecular vibrations as descriptors (Figure 5). For the selection of relevant vibrations, a mechanistic proposal is required a priori, commonly

Selective hydrolysis of α-oxo ketene N,S-acetals in water: switchable aqueous synthesis of β-keto thioesters and β-keto amides

• Haifeng Yu,
• Wanting Zhang,
• Xuejing Cui,
• Zida Liu,
• Xifu Zhang and
• Xiaobo Zhao

Beilstein J. Org. Chem. 2024, 20, 2225–2233, doi:10.3762/bjoc.20.190

• -en-1-ones 1a–l were smoothly hydrolyzed to produce a series of S-ethyl 3-oxo-3-arylpropanethioates 2a–l in excellent yield, wherein the electronic effects of electron-donating and electron-withdrawing groups on the aromatic ring adjacent to the carbonyl group did not impact the formation of the

• well as electron-withdrawing substituents on the two phenyl rings in compounds 1, such as methyl, methoxy, halogen atoms (F, Cl, Br, I), CF3 and SO2CH3, were well tolerated, and their electronic effects insignificantly impacted the formation of 3. Similarly, N-benzyl-3-oxo-3-phenylpropanamide (3w

Factors influencing the performance of organocatalysts immobilised on solid supports: A review

• Zsuzsanna Fehér,
• Dóra Richter,
• Gyula Dargó and
• József Kupai

Beilstein J. Org. Chem. 2024, 20, 2129–2142, doi:10.3762/bjoc.20.183

• more precise stereocontrol of the reaction [128][129][130][131][132]. Therefore, the difference in enantioselectivity values may be attributed to these electronic effects. Ultimately, the most favourable outcomes were achieved with catalyst C30 at 0 °C, with yields reaching up to 84% and enantiomeric

Multicomponent syntheses of pyrazoles via (3 + 2)-cyclocondensation and (3 + 2)-cycloaddition key steps

• Ignaz Betcke,
• Alissa C. Götzinger,
• Maryna M. Kornet and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2024, 20, 2024–2077, doi:10.3762/bjoc.20.178

• HOMO (diazo compound)–LUMO (alkyne) interaction during the 1,3-dipolar cycloaddition [163], Wu et al. showed that electronic effects in this strategy do not influence the yield. In addition, sterically demanding reactants could be used in the method. Enhanced yields were achieved by using NaOEt and

The Groebke–Blackburn–Bienaymé reaction in its maturity: innovation and improvements since its 21st birthday (2019–2023)

• Cristina Martini,
• Muhammad Idham Darussalam Mardjan and
• Andrea Basso

Beilstein J. Org. Chem. 2024, 20, 1839–1879, doi:10.3762/bjoc.20.162

Oxidative fluorination with Selectfluor: A convenient procedure for preparing hypervalent iodine(V) fluorides

• Samuel M. G. Dearman,
• Xiang Li,
• Yang Li,
• Kuldip Singh and
• Alison M. Stuart

Beilstein J. Org. Chem. 2024, 20, 1785–1793, doi:10.3762/bjoc.20.157

• contains two trifluoromethyl groups in the sidearm which could alter the electronic effects significantly. We therefore decided to prepare a small series of monocyclic trifluoro(aryl)-λ5-iodanes, where the sidearm substituents were changed stepwise from methyl to trifluoromethyl groups, so that we also

Ring opening of photogenerated azetidinols as a strategy for the synthesis of aminodioxolanes

• Henning Maag,
• Daniel J. Lemcke and
• Johannes M. Wahl

Beilstein J. Org. Chem. 2024, 20, 1671–1676, doi:10.3762/bjoc.20.148

• acids to the reaction mixture (see Supporting Information File 1 for further details). Finally, we decided to evaluate the electronic effects of the PG on the ring opening, which is why we opted to try the benzhydryl-protected substrate 3l in our envisioned transformation. Several recent publications

Generation of multimillion chemical space based on the parallel Groebke–Blackburn–Bienaymé reaction

• Evgen V. Govor,
• Vasyl Naumchyk,
• Ihor Nestorak,
• Dmytro S. Radchenko,
• Dmytro Dudenko,
• Yurii S. Moroz,
• Olexiy D. Kachkovsky and
• Oleksandr O. Grygorenko

Beilstein J. Org. Chem. 2024, 20, 1604–1613, doi:10.3762/bjoc.20.143

• }). Some of these results (e.g., on the reactivity of aminopyrimidine derivatives) were in accordance with the previous literature data [21][29]. Meanwhile, electronic effects of the substituents in the amino heterocycle reported in the previous works were somewhat contradictory. Whereas for the NO2 group

Phenotellurazine redox catalysts: elements of design for radical cross-dehydrogenative coupling reactions

• Alina Paffen,
• Christopher Cremer and
• Frederic W. Patureau

Beilstein J. Org. Chem. 2024, 20, 1292–1297, doi:10.3762/bjoc.20.112

• chemical stability, to such an extent that it could be in large part recovered at the end of the reaction (see previous study) [33]. In other words, PTeZ2 (2-methoxy substituent) features the best compromise in terms of electronic effects, which affect both the stability and reactivity of the key

Introduction of peripheral nitrogen atoms to cyclo-meta-phenylenes

• Koki Ikemoto and
• Hiroyuki Isobe

Beilstein J. Org. Chem. 2024, 20, 1207–1212, doi:10.3762/bjoc.20.103

• 3a and 3b resembled those of the hydrocarbon congeners, forming one-dimensional columns of stacked macrocycles (Figure 3b). The electronic effects of the nitrogen dopants in 3a were examined with X-ray charge density analyses [10][16]. For the crystal structures shown in Figure 3, we used a standard

Two-fold addition reaction of silylene to C₆₀: structural and electronic properties of a bis-adduct

• Masahiro Kako,
• Masato Kai,
• Masanori Yasui,
• Michio Yamada,
• Yutaka Maeda and
• Takeshi Akasaka

Beilstein J. Org. Chem. 2024, 20, 1179–1188, doi:10.3762/bjoc.20.100

• of 1 with the HOMO of 2a should be considered. Electrochemical measurements of 3 Cyclic voltammetry (CV) and differential pulse voltammetry (DPV) measurements were conducted to evaluate the electronic effects of the silylene addends in 3 (Figure 9). The oxidation processes of 3 were shown to be

Advancements in hydrochlorination of alkenes

• Daniel S. Müller

Beilstein J. Org. Chem. 2024, 20, 787–814, doi:10.3762/bjoc.20.72

• . Yadav demonstrated that a mixture of 8 equivalents of acetyl chloride with an equimolar amount of ethanol efficiently hydrochlorinates several reactive alkenes (Scheme 8) [54]. Electronic effects are noteworthy; p-methoxy-substituted styrene reacted within only 10 minutes to afford chloride 47, whereas

Enhanced reactivity of Li⁺@C₆₀ toward thermal [2 + 2] cycloaddition by encapsulated Li⁺ Lewis acid

• Hiroshi Ueno,
• Yu Yamazaki,
• Hiroshi Okada,
• Fuminori Misaizu,
• Ken Kokubo and
• Hidehiro Sakurai

Beilstein J. Org. Chem. 2024, 20, 653–660, doi:10.3762/bjoc.20.58

• electronic effects of the encapsulated Li+ Lewis acid, commonly exhibits significantly higher reactivity compared to empty C60. The much-enhanced reactivity often leads to the formation of multiadducts more notably than in the case of empty fullerenes, and hence, achieving the selective monofunctionalization

A laterally-fused N-heterocyclic carbene framework from polysubstituted aminoimidazo[5,1-b]oxazol-6-ium salts

• Andrew D. Gillie,
• Matthew G. Wakeling,
• Bethan L. Greene,
• Louise Male and
• Paul W. Davies

Beilstein J. Org. Chem. 2024, 20, 621–627, doi:10.3762/bjoc.20.54

• method and Sambvca V.2.0 software (Scheme 2) [29]. Although a similar value to that reported for IPrAuCl (%Vbur = 45.4%) [30] the steric map shows a very different steric environment on either side of the ligand. The AImOxIr(CO)2Cl complex 15 was targeted in order to assess the electronic effects of the

Entry to new spiroheterocycles via tandem Rh(II)-catalyzed O–H insertion/base-promoted cyclization involving diazoarylidene succinimides

• Alexander Yanovich,
• Anastasia Vepreva,
• Ksenia Malkova,
• Grigory Kantin and
• Dmitry Dar’in

Beilstein J. Org. Chem. 2024, 20, 561–569, doi:10.3762/bjoc.20.48

• carried out with different substituted propiolic acids 9 and DAS 1 are shown in Scheme 3. It can be noted that in the case of arylpropiolic acids, no significant influence of electronic effects of substituents in the aromatic ring was observed. In the case of the o-chloro derivative 2d the yield was

Synthesis of π-conjugated polycyclic compounds by late-stage extrusion of chalcogen fragments

• Aissam Okba,
• Pablo Simón Marqués,
• Kyohei Matsuo,
• Naoki Aratani,
• Hiroko Yamada,
• Gwénaël Rapenne and
• Claire Kammerer

Beilstein J. Org. Chem. 2024, 20, 287–305, doi:10.3762/bjoc.20.30

• sulfur extrusion [44]. It appeared that thiepines carrying sterically demanding substituents on the sulfur α-positions as well as annelated analogues show substantially increased lifetimes, owing to steric and electronic effects [45]. With these criteria in mind, a variety of thermally-stable annelated