Aryl iodane-induced cascade arylation–1,2-silyl shift–heterocyclization of propargylsilanes under copper catalysis

• Rasma Kroņkalne,
• Rūdolfs Beļaunieks,
• Armands Sebris,
• Anatoly Mishnev and
• Māris Turks

Beilstein J. Org. Chem. 2025, 21, 1984–1994, doi:10.3762/bjoc.21.154

• synthetic potential of iodane-mediated carbofunctionalization under copper catalysis. Keywords: arylation reactions; copper-catalysis; iodanes; propargylsilanes; 1,2-silyl shift; Introduction Highly electrophilic hypervalent iodine(III) reagents are considered as arene electrophilic synthons, making them

• the reagents of choice for arylation reactions, where an umpolung of reactivity is required [1]. Arylations employing diaryl-λ3-iodanes can be performed under metal-free [2] or metal-catalyzed conditions. For alkyne arylations [Cu] [3] or [Pd] catalysis [4][5][6] is typically employed. Internal

• analogs, that needed longer reaction times to reach full conversion (4 h for R = Ph, Me; 20 h for R = 3,5-(NO2)2C6H3). Conclusion In this work we have reported copper-catalyzed arylation reactions of propargylsilanes, using iodanes as the electrophilic aryl synthon equivalents. For internal nucleophile

Recent advances in organocatalytic atroposelective reactions

• Henrich Szabados and
• Radovan Šebesta

Beilstein J. Org. Chem. 2025, 21, 55–121, doi:10.3762/bjoc.21.6

Giese-type alkylation of dehydroalanine derivatives via silane-mediated alkyl bromide activation

• Perry van der Heide,
• Michele Retini,
• Fabiola Fanini,
• Giovanni Piersanti,
• Francesco Secci,
• Daniele Mazzarella,
• Timothy Noël and
• Alberto Luridiana

Beilstein J. Org. Chem. 2024, 20, 3274–3280, doi:10.3762/bjoc.20.271

• by Chatgilialoglu et al. [22] under non-photoredox conditions, MacMillan et al. [23] sparked renewed interest in silanes as XAT reagents by generating a tris(trimethylsilyl)silyl radical through photoredox catalysis for arylation reactions [22][23]. In 2018, Balsells et al. [24] reported a similar

Intramolecular C–H arylation of pyridine derivatives with a palladium catalyst for the synthesis of multiply fused heteroaromatic compounds

• Yuki Nakanishi,
• Shoichi Sugita,
• Kentaro Okano and
• Atsunori Mori

Beilstein J. Org. Chem. 2024, 20, 3256–3262, doi:10.3762/bjoc.20.269

• ; phosphine ligand; pyridine amides; Introduction Transition-metal-catalyzed synthetic reactions have recently attracted much attention in synthetic organic chemistry [1][2]. C–H Arylation reactions catalyzed by a transition metal are of particular interest because these reactions involve rather superior

Recent advances in transition-metal-free arylation reactions involving hypervalent iodine salts

• Ritu Mamgain,
• Kokila Sakthivel and
• Fateh V. Singh

Beilstein J. Org. Chem. 2024, 20, 2891–2920, doi:10.3762/bjoc.20.243

• concentrate on various arylation reactions involving carbon and other heteroatoms, encompassing rearrangement reactions in the absence of any metal catalyst, and summarize advancements made in the last five years. Keywords: arylation reaction; diaryliodonium salts; electrophilic arylation reagent; metal-free

• five to seven-membered cyclic compounds [47]. Arylation reactions using diaryliodonium salts can occur through four distinct mechanisms. First, the arylation can occur under metal-free conditions, involving the formation of a three-membered ring transition state through ligand coupling, leading to the

• solvent, whereas the arylation of ammonia was achieved by using ethyl acetate as solvent along with potassium carbonate as a base. Likewise, water was arylated using cesium carbonate as a base. The N-arylation reactions were performed under strict anhydrous conditions. The reported mechanistic hypothesis

Transition-metal-catalyst-free electroreductive alkene hydroarylation with aryl halides under visible-light irradiation

• Kosuke Yamamoto,
• Kazuhisa Arita,
• Masami Kuriyama and
• Osamu Onomura

Beilstein J. Org. Chem. 2024, 20, 1327–1333, doi:10.3762/bjoc.20.116

• the additional electron transfer to form the corresponding anions is a highly favorable pathway due to the more positive reduction potential of radicals than that of the starting halides [38], employing redox mediators enables the generated aryl radicals to participate in radical arylation reactions

Auxiliary strategy for the general and practical synthesis of diaryliodonium(III) salts with diverse organocarboxylate counterions

• Naoki Miyamoto,
• Daichi Koseki,
• Kohei Sumida,
• Elghareeb E. Elboray,
• Naoko Takenaga,
• Ravi Kumar and
• Toshifumi Dohi

Beilstein J. Org. Chem. 2024, 20, 1020–1028, doi:10.3762/bjoc.20.90

• triflate (TfO−) [14], tetrafluoroborate (BF4−) [15], tosylate (TsO−) [16], and others [17], has been extensively studied, as they play a key factor in the participation of iodonium salts in diverse arylation reactions. Recently, efficient syntheses of diaryliodonium(III) trifluoroacetates have been

• sterically hindered aryl(TMP)iodonium(III) carboxylates by combining the broad substrate scope of (hetero)aryl iodine(III) and carboxylic acids under mild conditions. Results and Discussion In the synthesis of diaryliodonium(III) salts and their application in arylation reactions, it is highly desirable to

Ortho-ester-substituted diaryliodonium salts enabled regioselective arylocyclization of naphthols toward 3,4-benzocoumarins

• Ke Jiang,
• Cheng Pan,
• Limin Wang,
• Hao-Yang Wang and
• Jianwei Han

Beilstein J. Org. Chem. 2024, 20, 841–851, doi:10.3762/bjoc.20.76

• this approach. Arylation reactions of aromatic compounds and reaction patterns of ortho-functionalized diaryliodonium salts. Mechanism study. Standard conditions: 1 (0.3 mmol, 1 equiv), 2 (0.33 mmol, 1.1 equiv), Cu(OAc)2 (10 mol %), DCE (2 mL), 80 °C, 3 hours. TEMPO = 2,2,6,6-tetramethylpiperidine-1

Application of N-heterocyclic carbene–Cu(I) complexes as catalysts in organic synthesis: a review

• Nosheen Beig,
• Varsha Goyal and
• Raj K. Bansal

Beilstein J. Org. Chem. 2023, 19, 1408–1442, doi:10.3762/bjoc.19.102

• arylaluminium reagents to five-, six-, and seven-membered β-substituted cyclic enones (Scheme 42). It is obvious that the NHC–Cu(I) complexes are generated in situ through transmetallation. For arylation reactions, Me2(Ar)Al reagents were used. The substrates having a variety of substituents (R = CH2Bn, n-Bu

Photoredox catalysis harvesting multiple photon or electrochemical energies

• Mattia Lepori,
• Simon Schmid and
• Joshua P. Barham

Beilstein J. Org. Chem. 2023, 19, 1055–1145, doi:10.3762/bjoc.19.81

• potentials whereas a second excitation with blue light yields the excited state *Rh-6G• that can reduce substrates with much more negative reduction potentials (Epred < −2.4 V vs SCE). The authors also demonstrated the applicability of Rh-6G for reductive arylation reactions (Figure 5D). While the use of PDI

Copper-catalyzed N-arylation of amines with aryliodonium ylides in water

• Kasturi U. Nabar,
• Bhalchandra M. Bhanage and
• Sudam G. Dawande

Beilstein J. Org. Chem. 2023, 19, 1008–1014, doi:10.3762/bjoc.19.76

• anti-inflammatory agent (Figure 1). Owing the importance of arylamines and their biological significance, the surge of development of innovative methods for their synthesis has been always an area of interest [12]. Specifically, the metal-mediated arylation reactions have witnessed significant

Pyridine C(sp²)–H bond functionalization under transition-metal and rare earth metal catalysis

• Haritha Sindhe,
• Malladi Mounika Reddy,
• Karthikeyan Rajkumar,
• Akshay Kamble,
• Amardeep Singh,
• Anand Kumar and
• Satyasheel Sharma

Beilstein J. Org. Chem. 2023, 19, 820–863, doi:10.3762/bjoc.19.62

• alkenylated product 109 (Scheme 21b). Arylation C-2 Arylation Owing to the remarkable role of aromatic C–H arylation reactions in organic synthesis abundant methods have been reported for aromatic C–H arylations using different arylating coupling partners, such as for instance, aryl halides. In 2014, using

Modular synthesis of 2-furyl carbinols from 3-benzyldimethylsilylfurfural platforms relying on oxygen-assisted C–Si bond functionalization

• Sebastien Curpanen,
• Per Reichert,
• Gabriele Lupidi,
• Giovanni Poli,
• Julie Oble and
• Alejandro Perez-Luna

Beilstein J. Org. Chem. 2022, 18, 1256–1263, doi:10.3762/bjoc.18.131

• -catalyzed cross-coupling reactions, such as arylation reactions catalyzed by Pd2(dba)3/CuI, as well as allylation and methylation reactions catalyzed by CuI⋅PPh3. C3-Benzyldimethylsilyl-appended furfurals are thus introduced as versatile platforms, providing a modular access to 3-substituted 2-furyl

• -catalyzed arylation reactions (Scheme 7). Fluoride-promoted arylation reactions of benzyldimethyl(alkenyl)silanes have been reported, and it is established that they proceed through the cleavage of the benzyl moiety from the benzyldimethylsilyl groups, leading to either dimethylsilanols or cyclic siloxanes

Efficient N-arylation of 4-chloroquinazolines en route to novel 4-anilinoquinazolines as potential anticancer agents

• Rodolfo H. V. Nishimura,
• Thiago dos Santos,
• Valter E. Murie,
• Luciana C. Furtado,
• Leticia V. Costa-Lotufo and
• Giuliano C. Clososki

Beilstein J. Org. Chem. 2021, 17, 2968–2975, doi:10.3762/bjoc.17.206

• ). As expected, substituents at the ortho-position of the anilines affected the N-arylation reactions due to the steric hindrance exerted by these groups. In fact, reactions with 2-methoxy-substituted N-methylaniline 9c were slower, but we obtained high conversions within 20 min under microwave heating

• the halogen substituents present in the anilines affected the N-arylation reactions. When we used 3-bromo-N-methylaniline (9f), we isolated derivatives 10k and 10l in 72 and 73% yields, respectively (Table 1, entries 11 and 12). Similarly, the reactions using 4-fluoro- or 3-fluoro-N-methylaniline (9g

• biologically active molecules are currently being investigated in our laboratories. Some antitumor agents containing the 4-anilinoquinazoline moiety. Examples of N-arylation reactions using 4-chloroquinazolines as substrates. Synthesis of verubulin analog. Synthesis of 4-chloro-6-halo-2-phenylquinazolines 8a

A visible-light-induced, metal-free bis-arylation of 2,5-dichlorobenzoquinone

• Pieterjan Winant and
• Wim Dehaen

Beilstein J. Org. Chem. 2021, 17, 2315–2320, doi:10.3762/bjoc.17.149

• be a challenging endeavor. As conventional methods, e.g., the Heck reaction are incompatible with quinones [15], a large subset of research recently focused on radical-based CH-arylation reactions. In 2011, Baran published a seminal paper that relied on using a AgNO3/K2S2O8 induced homolytic

• , aryldiazonium salts have long played an essential role as radical precursors [20]. Their use in CH-arylation reactions of olefins, catalyzed by copper salts, was first published by Meerwein in 1939 [21]. Recently, we published a Meerwein arylation/cyclization sequence to benzofuropyridine derivatives in this

Preparation of mono-substituted malonic acid half oxyesters (SMAHOs)

• Tania Xavier,
• Sylvie Condon,
• Christophe Pichon,
• Erwan Le Gall and
• Marc Presset

Beilstein J. Org. Chem. 2021, 17, 2085–2094, doi:10.3762/bjoc.17.135

• usually achieved by a nucleophilic substitution of an alkyl halide by the deprotonated malonate [12][13][14][15][16][17][18][19], but other strategies could be envisioned: Cu-catalyzed arylation reactions for aryl-substituted MAHOs [20][21][22][23]; Knoevenagel/reduction sequences for benzyl-substituted

CF₃-substituted carbocations: underexploited intermediates with great potential in modern synthetic chemistry

• Anthony J. Fernandes,
• Armen Panossian,
• Bastien Michelet,
• Agnès Martin-Mingot,
• Frédéric R. Leroux and
• Sébastien Thibaudeau

Beilstein J. Org. Chem. 2021, 17, 343–378, doi:10.3762/bjoc.17.32

• compounds 161 in high yield (Scheme 40, top). The reaction of CF3-substituted 1,3-diketones 165a–d in TfOH was also deeply investigated by Klumpp et al. [101]. The syn-indanes 166a–d could cleanly be generated after successive well-defined arylation reactions via 167 (Scheme 40, bottom). Moreover, the CF3

When metal-catalyzed C–H functionalization meets visible-light photocatalysis

• Lucas Guillemard and
• Joanna Wencel-Delord

Beilstein J. Org. Chem. 2020, 16, 1754–1804, doi:10.3762/bjoc.16.147

Highly selective Diels–Alder and Heck arylation reactions in a divergent synthesis of isoindolo- and pyrrolo-fused polycyclic indoles from 2-formylpyrrole

• Carlos H. Escalante,
• Eder I. Martínez-Mora,
• Carlos Espinoza-Hicks,
• Alejandro A. Camacho-Dávila,
• Fernando R. Ramos-Morales,
• Francisco Delgado and
• Joaquín Tamariz

Beilstein J. Org. Chem. 2020, 16, 1320–1334, doi:10.3762/bjoc.16.113

• - and pyrrolo-fused polycyclic indoles is herein described, starting from 2-formylpyrrole and employing Diels–Alder and Heck arylation reactions. 3-(N-Benzyl-2-pyrrolyl)acrylates and 4-(pyrrol-2-yl)butenones underwent a highly endo-Diels–Alder cycloaddition with maleimides to furnish octahydropyrrolo

Photocatalysis with organic dyes: facile access to reactive intermediates for synthesis

• Stephanie G. E. Amos,
• Marion Garreau,
• Luca Buzzetti and
• Jerome Waser

Beilstein J. Org. Chem. 2020, 16, 1163–1187, doi:10.3762/bjoc.16.103

• trapping of the ensuing C(sp3) radical with the deuterated or tritiated thiol results in the incorporation of deuterium or tritium in multiple positions within the product 9.3. C(sp2) radicals Aryl radicals Considering the importance of arylation reactions in organic synthesis [61], aryl radicals are

Accelerating fragment-based library generation by coupling high-performance photoreactors with benchtop analysis

• Quentin Lefebvre,
• Christophe Salomé and
• Thomas C. Fessard

Beilstein J. Org. Chem. 2020, 16, 982–988, doi:10.3762/bjoc.16.87

• Quentin Lefebvre Christophe Salome Thomas C. Fessard SpiroChem AG, Rosental area, WRO-1047-3, Mattenstrasse 24, 4058 Basel, Switzerland 10.3762/bjoc.16.87 Abstract Herein we report a workflow coupling photoredox-nickel dual-catalyzed N-arylation reactions to benchtop analysis for the efficient

Efficient synthesis of 3,6,13,16-tetrasubstituted-tetrabenzo[a,d,j,m]coronenes by selective C–H/C–O arylations of anthraquinone derivatives

• Seiya Terai,
• Yuki Sato,
• Takuya Kochi and
• Fumitoshi Kakiuchi

Beilstein J. Org. Chem. 2020, 16, 544–550, doi:10.3762/bjoc.16.51

• reactions have been increasingly utilized in recent years for the rapid expansion of the aromatic frameworks [10][11][12][13][14][15]. We have been working on the efficient syntheses of PAH derivatives based on the ruthenium-catalyzed C–H/C–O arylation reactions developed in our group [16][17][18][19][20

• groups to form biaryl frameworks. Traditionally, transition-metal-catalyzed cross-coupling reactions of aryl halides or pseudohalides with arylmetal reagents have been employed for the connection of two aryl units [5][6][7][8][9]. However, in search of more efficient synthetic routes, C–H arylation

Recent advances on the transition-metal-catalyzed synthesis of imidazopyridines: an updated coverage

• Gagandeep Kour Reen,
• Ashok Kumar and
• Pratibha Sharma

Beilstein J. Org. Chem. 2019, 15, 1612–1704, doi:10.3762/bjoc.15.165

Synthesis of aryl sulfides via radical–radical cross coupling of electron-rich arenes using visible light photoredox catalysis

• Amrita Das,
• Mitasree Maity,
• Simon Malcherek,
• Burkhard König and
• Julia Rehbein

Beilstein J. Org. Chem. 2018, 14, 2520–2528, doi:10.3762/bjoc.14.228

• charge transfer using Cs2CO3 as base [41]. Two recent reports showed the synthesis of C-3 sulfenylated indoles and 3-sulfenylimidazopyridine via C–H functionalization using Rose Bengal as photocatalyst [42][43]. In general, the arylation reactions use the reductive cycle of the photocatalyst and for this

Polysubstituted ferrocenes as tunable redox mediators

• Sven D. Waniek,
• Jan Klett,
• Christoph Förster and
• Katja Heinze

Beilstein J. Org. Chem. 2018, 14, 1004–1015, doi:10.3762/bjoc.14.86

• syntheses [17][18][19][20][21][22][23][24][25][26][27][28]. Tuning of the electrochemical potential of substituted ferrocenium salts promoted a selective oxidative bicyclization reaction under mild conditions (Scheme 1a) [27]. Ferrocene and decamethylferrocene act as redox catalysts in Meerwein arylation

• reactions [29], borylations of arenediazonium salts [30] and in C–H imidation reactions of (hetero)arenes [31] (Scheme 1b,c). Ferrocene has been used as redox mediator for the electrochemical modification of carbon surfaces via electrochemical oxidation of carboxylates [32][33], as mediator for