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

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

• of 74% for bromine 2 and 78% for iodo starting material 3 (Table 3) [24]. To overcome the problems of poor yields in the arylation of N-acetyl diazocines via Stille coupling we used Suzuki–Miyaura reactions of the diazocines 2 and 3 with different arylboronic acids [25][26]. There are several

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

• + with the formation of 58 in 95% yield (Scheme 14). Similarly, the photoinduced aerobic oxidative hydroxylation of arylboronic acids 59 has been successfully accomplished. Since this reaction does not depend on the presence of singlet oxygen, it confirmed the electron-transfer capability of the DMQA

• the radical cation iPr2NEt•+ (iPr2NEt/iPr2NEt•+ = +0.72 V vs SCE) and the reduction of O2 by the reduced photocatalyst, forming the superoxide radical anion O2•− (O2/O2•− = −0.57 V vs SCE). This latter can then react with arylboronic acids 59 to give, after hydrolysis, phenol derivatives 60. Other

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

Recent advances in electrochemical copper catalysis for modern organic synthesis

• Yemin Kim and
• Won Jun Jang

Beilstein J. Org. Chem. 2025, 21, 155–178, doi:10.3762/bjoc.21.9

• reactions are essential synthetic methodologies. The discovery of Chan–Lam coupling reactions, which use arylboronic acids and N-nucleophiles, provided a C–N bond-forming protocol using copper catalysis, offering a complementary method to noble transition-metal catalysis [78]. Recently, dual-catalytic

• systems combining copper catalysis with electrocatalysis have been developed to avoid the use of chemical oxidants. Thus, the substrate scope was expanded to include electron-deficient arylboronic acids. In 2019, Gale-Day et al. developed electrocatalytic Chan–Lam couplings of arylboronic acids with

• alkylamines with arylboronic acids, achieving high yields. Mechanistic studies revealed that the mediator plays multiple roles, including rapidly oxidizing low-valent Cu intermediates to maintain high Cu(II) concentrations, removing Cu metal from the cathode to regenerate the active Cu catalyst, revealing the

Nickel-catalyzed cross-coupling of 2-fluorobenzofurans with arylboronic acids via aromatic C–F bond activation

• Takeshi Fujita,
• Haruna Yabuki,
• Ryutaro Morioka,
• Kohei Fuchibe and
• Junji Ichikawa

Beilstein J. Org. Chem. 2025, 21, 146–154, doi:10.3762/bjoc.21.8

• , Ibaraki 305-8571, Japan Sagami Chemical Research Institute, 2743-1 Hayakawa, Ayase, Kanagawa 252-1193, Japan 10.3762/bjoc.21.8 Abstract 2-Fluorobenzofurans underwent efficient nickel-catalyzed coupling with arylboronic acids through the activation of aromatic C–F bonds. This method allowed us to

• coupling reactions of aromatic C–F and C–Br bonds with arylboronic acids. Keywords: arylboronic acid; benzofuran; C–F bond activation; cross-coupling; nickel; Introduction The metal-catalyzed activation of aromatic carbon–fluorine (C–F) bonds is widely recognized as a challenging task in synthetic

• (Scheme 1c). In this study, we demonstrate nickel-catalyzed defluorinative cross-coupling [22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37] of 2-fluorobenzofurans 1 with arylboronic acids 2 at ambient temperature, with nickelacyclopropanes E serving as crucial intermediates for the

Synthesis of acenaphthylene-fused heteroarenes and polyoxygenated benzo[j]fluoranthenes via a Pd-catalyzed Suzuki–Miyaura/C–H arylation cascade

• Merve Yence,
• Dilgam Ahmadli,
• Damla Surmeli,
• Umut Mert Karacaoğlu,
• Sujit Pal and
• Yunus Emre Türkmen

Beilstein J. Org. Chem. 2024, 20, 3290–3298, doi:10.3762/bjoc.20.273

• 1,8-diiodonaphthalene (12) and a broad range of arylboronic acids and esters to afford substituted fluoranthenes 13 in good to high yields (Scheme 1d) [43]. In that work, we had only one example of a heterocyclic fluoranthene analogue where the use of 4-pyridylboronic acid provided the corresponding

• ]fluoranthene 28. Investigation of different thiophene-3-ylboronic acid and esters in the synthesis of 15a. Investigation of various (hetero)arylboronic acids and esters in the Suzuki–Miyaura/C–H arylation sequence. Supporting Information Supporting Information File 56: Experimental procedures

Transition-metal-free decarbonylation–oxidation of 3-arylbenzofuran-2(3H)-ones: access to 2-hydroxybenzophenones

• Bhaskar B. Dhotare,
• Seema V. Kanojia,
• Chahna K. Sakhiya,
• Amey Wadawale and
• Dibakar Goswami

Beilstein J. Org. Chem. 2024, 20, 2655–2667, doi:10.3762/bjoc.20.223

• oxidative coupling of salicylaldehyde with arylboronic acids to successfully produce 2-hydroxybenzophenones [14]. Recently, a Ni-catalyzed decarbonylation–oxidation of 3-arylbenzofuran-2(3H)-ones emerged as an innovative route to access 2-hydroxybenzophenones [2]. The use of transition metals poses

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

• pyrazole synthesis is the synthetic accessibility of hydrazines. To circumvent this limitation, arylboronic acids can be coupled with Boc-protected diimide 23 under copper catalysis to form the hydrazine precursor in situ. Subsequent removal of the Boc groups and cyclocondensation with 1,3-dicarbonyl

• to synthesize 3,4-substituted pyrazoles 57 from iodochromones 55, arylboronic acids 56, and hydrazines (Scheme 16) [72]. During the Suzuki step, electronically and sterically diverse substituents were successfully coupled to chromones. Notably, a single regioisomer is formed when methylhydrazine is

• = Cl, Br). The resulting 4-halopyrazoles 111 can either be isolated or undergo further Suzuki coupling with arylboronic acids. Both couplings use the Pd catalyst in a sequential fashion. To increase the yields, both cyclization and Suzuki coupling are carried out with microwave support. Some of the

Mono or double Pd-catalyzed C–H bond functionalization for the annulative π-extension of 1,8-dibromonaphthalene: a one pot access to fluoranthene derivatives

• Nahed Ketata,
• Linhao Liu,
• Ridha Ben Salem and
• Henri Doucet

Beilstein J. Org. Chem. 2024, 20, 427–435, doi:10.3762/bjoc.20.37

• -worker described the reaction of 1,8-diiodonaphthalene with arylboronic acids using PdCl2(dppf) as catalyst for the synthesis of various substituted fluoranthenes (Scheme 1a) [19]. In 2009, Quimby and Scott reported the use of 5,6-dichloro-1,2-dihydroacenaphthylene for the preparation of fluoranthene

• via Suzuki coupling with arylboronic acids (Scheme 4). Using the same reaction conditions as for the double activation of C–H bonds described in Scheme 2, the reaction of 1,8-dibromonaphthalene with 4-ethoxybenzeneboronic acid gave the desired 8-ethoxyfluoranthene (19) in 69% yield. The influence of a

• range of para-substituents on the aryl unit of the arylboronic acids was then evaluated (Scheme 4). Methyl, ester and nitrile substituents were well tolerated, giving rise to products 20, 22, and 23 in yields ranging from 71% to 77%. A 4-chloro substituent was also well tolerated, providing product 21

Mechanisms for radical reactions initiating from N-hydroxyphthalimide esters

• Carlos R. Azpilcueta-Nicolas and
• Jean-Philip Lumb

Beilstein J. Org. Chem. 2024, 20, 346–378, doi:10.3762/bjoc.20.35

• -catalyzed decarboxylative functionalizations employing RAEs have been established (Scheme 24). Baran and co-workers have reported arylation protocols (Scheme 24A) using arylzinc reagents [84][85], Grignard reagents [85] and arylboronic acids [86], as well as decarboxylative alkenylation [87] (Scheme 24B

Synthesis and biological evaluation of Argemone mexicana-inspired antimicrobials

• Jessica Villegas,
• Bryce C. Ball,
• Katelyn M. Shouse,
• Caleb W. VanArragon,
• Ashley N. Wasserman,
• Hannah E. Bhakta,
• Allen G. Oliver,
• Danielle A. Orozco-Nunnelly and
• Jeffrey M. Pruet

Beilstein J. Org. Chem. 2023, 19, 1511–1524, doi:10.3762/bjoc.19.108

• of two substituted arylboronic acids, followed by N-methylation, and final ring-closure via Bischler–Napieralski conditions [45][47][48]. These steps provided chelerythrine variants C1–C4, with structural variability stemming from the initial substituted tetralone (R1/R2) and/or the arylboronic acid

N-Sulfenylsuccinimide/phthalimide: an alternative sulfenylating reagent in organic transformations

• Fatemeh Doraghi,
• Seyedeh Pegah Aledavoud,
• Mehdi Ghanbarlou,
• Bagher Larijani and
• Mohammad Mahdavi

Beilstein J. Org. Chem. 2023, 19, 1471–1502, doi:10.3762/bjoc.19.106

• selectively transfer the acyl or acylthio moieties. Arylboronic acids 74 and amines 76 were suitable for the acyl transfer and led to ketones 78 and amides 80 as the desired products. While, Grignard reagents 75 and thiols 77 acted as soft nucleophiles and resulted in thioesters 79 and acyl disulfides 81

Consecutive four-component synthesis of trisubstituted 3-iodoindoles by an alkynylation–cyclization–iodination–alkylation sequence

• Nadia Ledermann,
• Alae-Eddine Moubsit and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2023, 19, 1379–1385, doi:10.3762/bjoc.19.99

• alkynyl-substituted 3-iodoindole 6 as product in 42% isolated yield in the sense of a pseudo-five-component reaction (Scheme 3). Finally, the 3-iodoindole 5a and arylboronic acids 7 were employed in a standard Suzuki protocol with cesium carbonate as a base to give rise to the formation of 1,2,3

• -dibromoaniline (1c); bwith 4-bromo-2-iodoaniline (1d)). Consecutive double alkynylation–cyclization–iodination–alkylation pseudo-five-component synthesis of 5-phenylethynyl-1,2-disubstituted 3-iodoindole 6. Suzuki coupling of 3-iodoindole 5a with arylboronic acids 7 to give 1,2,3-trisubstituted indoles 8

Palladium-catalyzed enantioselective three-component synthesis of α-arylglycine derivatives from glyoxylic acid, sulfonamides and aryltrifluoroborates

• Bastian Jakob,
• Nico Schneider,
• Luca Gengenbach and
• Georg Manolikakes

Beilstein J. Org. Chem. 2023, 19, 719–726, doi:10.3762/bjoc.19.52

• sterically hindered arylboronic acids. Herein, we report an improved version of this palladium-catalyzed enantioselective three-component reactions using aryltrifluoroborates as replacement of the arylboronic acid building block (Scheme 1d). The broader scope of this 2nd generation protocol is exploiting a

• . Among different boronic acid derivatives, we identified aryltrifluoroborates as most promising candidates for the slow generation of the corresponding arylboronic acids under our slightly acid reaction conditions [24]. Therefore, we performed two initial control experiments. The reaction of potassium

• to the formation of the arylgylcine in trace amounts (Table 1, entries 2–5). Contrary to our previous report with arylboronic acids, the presence of air is highly detrimental to the reaction outcome (Table 1, entry 6). Therefore, inert conditions were employed throughout all subsequent studies

Enolates ambushed – asymmetric tandem conjugate addition and subsequent enolate trapping with conventional and less traditional electrophiles

• Péter Kisszékelyi and
• Radovan Šebesta

Beilstein J. Org. Chem. 2023, 19, 593–634, doi:10.3762/bjoc.19.44

• complex molecules by further transformations. Similarly, Huang et al. have recently published their work on the Rh-bod complex-catalyzed highly stereoselective tandem arylation/aldol cyclization [95]. The conjugate addition of arylboronic acids to acyclic α,β-unsaturated ketones 147 with sequential

Transition-metal-catalyzed domino reactions of strained bicyclic alkenes

• Austin Pounder,
• Eric Neufeld,
• Peter Myler and
• William Tam

Beilstein J. Org. Chem. 2023, 19, 487–540, doi:10.3762/bjoc.19.38

• 17 (Scheme 4) [36]. While broadly successful, when electron-deficient arylboronic acids were used, slightly diminished yields were observed. Moreover, when 3-hexyne was used, the reaction failed to afford any product. The reaction likely begins similarly to Cheng’s 2003 report (Scheme 1) [31] where

• azaspirotricyclic alkenes 176 using arylboronic acids 177 (Scheme 32) [79]. This reaction proceeded well with a variety of ester substituents on the nitrogens of the azaspirotricyclic alkenes. The authors proposed this reaction proceeds first through a transmetalation of the arylboronic acid 177a with the Rh(I

Synthesis of novel alkynyl imidazopyridinyl selenides: copper-catalyzed tandem selenation of selenium with 2-arylimidazo[1,2-a]pyridines and terminal alkynes

• Mio Matsumura,
• Kaho Tsukada,
• Kiwa Sugimoto,
• Yuki Murata and
• Shuji Yasuike

Beilstein J. Org. Chem. 2022, 18, 863–871, doi:10.3762/bjoc.18.87

• ]. Guo, Han and Ma et al. also performed the synthesis of aryl imidazopyridinyl selenides in the presence of Ag2CO3 (2 equiv) and Cs2CO3 (2 equiv) using the CuI/1,10-phenanthroline catalytic system by replacing the aryl group donor with arylboronic acids [23]. Zhou et al. reported the reaction of Se

• powder with imidazopyridine and aryl iodides or alkyl halides in the presence of Na2CO3 (2 equiv) using the NiBr2/2,2-bipyridine system to give aryl or alkyl imidazopyridinyl selenides [24]. In these reactions, aryl iodides, arylboronic acids, and alkyl halides are coupled with Se powder to form diaryl

Substituent effect on TADF properties of 2-modified 4,6-bis(3,6-di-tert-butyl-9-carbazolyl)-5-methylpyrimidines

• Irina Fiodorova,
• Tomas Serevičius,
• Rokas Skaisgiris,
• Saulius Juršėnas and
• Sigitas Tumkevicius

Beilstein J. Org. Chem. 2022, 18, 497–507, doi:10.3762/bjoc.18.52

• of aryl moieties into methylthio-substituted nitrogen heterocycles such as tCBz-mPYR are a Ni(0)-catalyzed cross-coupling reaction with Grignard reagents [34][36] or the Liebeskind–Srogl reaction employing arylboronic acids [37][38][39]. Taking into account a large assortment of arylboronic acids and

Borylated norbornadiene derivatives: Synthesis and application in Pd-catalyzed Suzuki–Miyaura coupling reactions

• Robin Schulte and
• Heiko Ihmels

Beilstein J. Org. Chem. 2022, 18, 368–373, doi:10.3762/bjoc.18.41

• derivatives may be metalated in a Li–halogen exchange reaction [27]. In another versatile approach, arylation and alkenylation reactions of the norbornadiene may be accomplished with a Suzuki–Miyaura coupling reaction. In this case, halogenated norbornadienes react with arylboronic acids or their esters to

• with Pd2(dba)3/(t-Bu)3PHBF4 as catalytic system and CsF as additive in THF at room temperature, because these conditions have been shown to be well-suitable for Suzuki–Miyaura reactions of halogen-substituted norbornadiene derivatives with arylboronic acids [28]. However, under these conditions the

Iridium-catalyzed hydroacylation reactions of C1-substituted oxabenzonorbornadienes with salicylaldehyde: an experimental and computational study

• Angel Ho,
• Austin Pounder,
• Krish Valluru,
• Leanne D. Chen and
• William Tam

Beilstein J. Org. Chem. 2022, 18, 251–261, doi:10.3762/bjoc.18.30

• (EDGs) led to naphthol compounds 9, while electron-withdrawing groups (EWGs) led to the anticipated ring-opened 1,1,2-trisubstituted naphthalene framework 10 [61]. On the other hand, Edmunds and co-workers described a ring-opening reaction of C1-substituted OBDs 5 with arylboronic acids that was

Ligand-dependent stereoselective Suzuki–Miyaura cross-coupling reactions of β-enamido triflates

• Tomáš Chvojka,
• Athanasios Markos,
• Svatava Voltrová,
• Radek Pohl and
• Petr Beier

Beilstein J. Org. Chem. 2021, 17, 2657–2662, doi:10.3762/bjoc.17.179

• was ruled out because the treatment of 2ca under conditions leading to inversion of the configuration did not affect the ratio between the resulting enamides. Conclusion In conclusion, the stereoselective outcome of the Suzuki cross-coupling of vinyl triflates 1 with arylboronic acids was found to be

• configuration of the double bond were formed preferably. Both conditions were applied to a range of arylboronic acids and (Z)-β-enamido triflates. A: Synthesis of (Z)-β-enamido triflates and subsequent stereoselective cross-coupling reactions. B: Ligand-controlled stereoselective synthesis of β,β-diaryl

Synthesis and investigation on optical and electrochemical properties of 2,4-diaryl-9-chloro-5,6,7,8-tetrahydroacridines

• Najeh Tka,
• Mohamed Adnene Hadj Ayed,
• Mourad Ben Braiek,
• Mahjoub Jabli and
• Peter Langer

Beilstein J. Org. Chem. 2021, 17, 2450–2461, doi:10.3762/bjoc.17.162

• equivalents of K3PO4 in toluene at 100 °C for 4 hours. With our optimized conditions in hand, we examined the scope of the reaction of 2 with other arylboronic acids 3b–g (Scheme 2). As expected, we found that electron-donating groups located in the arylboronic acid improved the yield. The cross-coupling of 2

• with arylboronic acids 3b and 3d, bearing a methoxy group in position 2 or 4, afforded the corresponding products 4b and 4d in excellent yields. Arylboronic acids containing an alkyl group in different positions afforded good yields for products 4e and 4g. With the substrate containing a

Recent advances in the syntheses of anthracene derivatives

• Giovanni S. Baviera and
• Paulo M. Donate

Beilstein J. Org. Chem. 2021, 17, 2028–2050, doi:10.3762/bjoc.17.131

• monofunctionalized naphthyl substrates. These authors demonstrated that the rhodium-catalyzed oxidative 1:2 coupling reactions of arylboronic acids 7 with alkyne 8 occurred in the presence of a copper–air oxidant, to give the corresponding 1,2,3,4-tetrasubtituted anthracene derivatives 9a and 9b (Scheme 1) [34

• this review can serve to guide and to inspire future advances in synthetic organic chemistry for this kind of polycyclic compounds. Examples of anthracene derivatives and their applications. Rhodium-catalyzed oxidative coupling reactions of arylboronic acids with internal alkynes. Rhodium-catalyzed

• presence of Pd(PPh3)4 as catalyst, was inefficient with the chloro-substituted aryl substrates. However, the use of Pd-PEPPSI-iPr as catalyst solved this problem. By using this catalyst, the authors obtained 1,8-diarylanthracenes 64a–f in good yields (52–77%) from reactions of the corresponding arylboronic

On the application of 3d metals for C–H activation toward bioactive compounds: The key step for the synthesis of silver bullets

• Renato L. Carvalho,
• Amanda S. de Miranda,
• Mateus P. Nunes,
• Roberto S. Gomes,
• Guilherme A. M. Jardim and
• Eufrânio N. da Silva Júnior

Beilstein J. Org. Chem. 2021, 17, 1849–1938, doi:10.3762/bjoc.17.126

• inspired by the biocatalytic action of the cytochrome P-450 cycle, which is driven by a reductase or bioreductant, and presented high versatility in incorporating both aldehyde and ketone functionalities into unprotected arylboronic acids. The reaction consists of using a porphyrin-based iron catalyst, and