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

• overview of arylation of carbon and heteroatom substrates via diaryliodonium salts in metal-free conditions. This review emphasizes the significance and potential of DIASs in contemporary organic chemistry. Review C-Arylation Over the past decade, there has been a surge of interest in metal-catalyzed C

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

• enabling controlled bond activations [45]. Regarding the reductive C–C arylation, the application of the xanthene dye rhodamine 6G (Rh-6G) as a catalyst for the reduction of heteroarenes bearing two or three bromine atoms (e.g., 6) under irradiation with green light (λ = 530 nm) gave monosubstituted

Facile and diastereoselective arylation of the privileged 1,4-dihydroisoquinolin-3(2H)-one scaffold

• Dmitry Dar’in,
• Grigory Kantin,
• Alexander Bunev and
• Mikhail Krasavin

Beilstein J. Org. Chem. 2022, 18, 1070–1078, doi:10.3762/bjoc.18.109

• in the literature. While pondering possible solutions to fill this void, we drew inspiration in our recent success achieving direct Brønsted acid-catalyzed C-arylation of 4-diazo-isoquinoline-1,3-diones 7 [9] which are, in turn, obtainable via the Regitz diazo transfer reaction onto readily available

• optimum conditions for the C-arylation of diazo substrates 10 (60 equiv ArH, 1.5 equiv TfOH, DCM, rt, 15 min), we proceeded to investigate the scope of this transformation for 4-diazo-3(2H)-isoquinolones 10a–s as well as various arenes (Scheme 3). In all cases, this (generally high-yielding

• ) transformation resulted in the highly diastereoselective formation of C-arylation products 10 which in some cases was accompanied by a regioisomer formation (with respect to the entering arene moiety) and the formation of 3-isoquinolones 15 (isolated and characterized in several instances). Not unexpectedly

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

• ][42][43][44]. Various copper salts have been used as Lewis acid in homogeneous catalysis. CuO nanoparticles (NPs) were used for C–N, C–S, C–O cross-coupling reactions and C-arylation. Recently, exploiting the cross-coupling tendency of CuO NPs, Reddy et al. have reported their use as a heterogeneous

One-pot preparation of 4-aryl-3-bromocoumarins from 4-aryl-2-propynoic acids with diaryliodonium salts, TBAB, and Na₂S₂O₈

• Teppei Sasaki,
• Katsuhiko Moriyama and
• Hideo Togo

Beilstein J. Org. Chem. 2018, 14, 345–353, doi:10.3762/bjoc.14.22

• -alkynoates with N-bromosuccinimide (NBS) at rt [34], where those reactions proceed via radical spiro-cyclization and then radical 1,2-carboxyl group migration, were reported. On the other hand, diaryliodonium salts are very useful for the C-arylation of active CH groups, the O-arylation of OH groups, and the

Synthesis of benzannelated sultams by intramolecular Pd-catalyzed arylation of tertiary sulfonamides

• Valentin A. Rassadin,
• Mirko Scholz,
• Anastasiia A. Klochkova,
• Armin de Meijere and
• Victor V. Sokolov

Beilstein J. Org. Chem. 2017, 13, 1932–1939, doi:10.3762/bjoc.13.187

• Göttingen, Germany 10.3762/bjoc.13.187 Abstract A new and efficient approach to five- and six-membered benzannelated sultams by intramolecular C-arylation of tertiary 1-(methoxycarbonyl)methanesulfonamides under palladium catalysis is described. In case of the α-toluenesulfonamide derivative, an unexpected

• trifluoroacetic acid [36]. Indeed, when 10a was treated with CF3CO2H in refluxing dichloromethane for 3 days, the deprotected sultam 23 was isolated in a good yield of 72% (Scheme 7). Conclusion In conclusion, the intramolecular palladium-catalyzed C-arylation of tertiary 1-(methoxycarbonyl)methanesulfonanilides

Silyl-protective groups influencing the reactivity and selectivity in glycosylations

• Mikael Bols and
• Christian Marcus Pedersen

Beilstein J. Org. Chem. 2017, 13, 93–105, doi:10.3762/bjoc.13.12

• , the ability of the bulky silyl groups to alter the conformation of the glycosyl-donor ring can be used to control the selectivity. Suzuki and collaborators showed that the C-arylation reactions with the 3,4-O-di(tert-butyldiphenylsilyl)-protected acetate 56 led to the α-glycoside 58 with high

• thioglycoside 41. Regio- and stereoselective glycosylation using the superarmed thioglycoside donor 20. Superarmed donors used for C-arylation and the dependence of the size of the silylethers on the stereochemical outcome. β-Selective glucosylation with TIPS-protected glucosyl donors. The α-face is shielded by

Recent advances in copper-catalyzed asymmetric coupling reactions

• Fengtao Zhou and
• Qian Cai

Beilstein J. Org. Chem. 2015, 11, 2600–2615, doi:10.3762/bjoc.11.280

• synthesis of chiral biphenyl diphosphine ligands by means of an intramolecular Ullmann coupling with the introduction of chiral bridged ethers. Catalytic asymmetric C–C coupling In 1929, Hurtley reported the first example of a C-arylation reaction of malonic esters with 2-bromobenzoic acid using a catalytic

Synthesis of diverse indole libraries on polystyrene resin – Scope and limitations of an organometallic reaction on solid supports

• Kerstin Knepper,
• Sylvia Vanderheiden and
• Stefan Bräse

Beilstein J. Org. Chem. 2012, 8, 1191–1199, doi:10.3762/bjoc.8.132

• ], palladium-catalyzed indole synthesis [34][35][36][37][38][39][40], cycloaddition strategies [41], C-arylation of substituted acetonitriles or 1,3-dicarbonyl compounds [42], halocyclization [43][44] and finally, reduction of ortho-fluoro-nitroarenes [42]. The significant biological properties and the

Amines as key building blocks in Pd-assisted multicomponent processes

• Didier Bouyssi,
• Nuno Monteiro and
• Geneviève Balme

Beilstein J. Org. Chem. 2011, 7, 1387–1406, doi:10.3762/bjoc.7.163

• a Pd-catalyzed cascade sequence, involving an alkenyl amination, a C-arylation and a subsequent intramolecular N-arylation, was developed by Barluenga and coworkers for the preparation of indole derivatives 68 [37]. Here, equimolecular amounts of haloalkene 65, o-dihaloarene 66, and amines are mixed

• -alkynylindoles through a Pd-catalyzed Sonogashira/double C–N coupling reaction. Synthesis of indoles through a Pd-catalyzed sequential alkenyl amination/C-arylation/N-arylation. Synthesis of N-aryl-2-benzylpyrrolidines through a sequential N-arylation/carboamination reaction. Synthesis of phenothiazine

• basic media. A subsequent Pd-mediated intermolecular alkylation with the dihalogeno substrate followed by an intramolecular N-arylation furnished 2-substituted indoles 68. In this cascade reaction, the palladium catalyst intervenes in three different coupling reactions: Intermolecular N-alkenylation, C

C-Arylation reactions catalyzed by CuO-nanoparticles under ligand free conditions

• Mazaahir Kidwai,
• Saurav Bhardwaj and
• Roona Poddar

Beilstein J. Org. Chem. 2010, 6, No. 35, doi:10.3762/bjoc.6.35

• Mazaahir Kidwai Saurav Bhardwaj Roona Poddar Green Research Laboratory, Department ofChemistry, University of Delhi, Delhi, India 110007 10.3762/bjoc.6.35 Abstract CuO-nanoparticles were found to be an excellent heterogeneous catalyst for C-arylation of active methylene compounds using various

• aryl halides. The products were obtained in good to excellent yield. The catalyst can be recovered and reused for four cycles with almost no loss in activity. Keywords: active methylene compounds; C-arylation; heterogeneous catalyst; recyclability; Introduction Carbon-carbon (C–C) bond formation is

• one of the most important reactions in organic synthesis [1][2][3]. The resulting compounds formed from C–C coupling are valuable synthons in organic synthesis [4][5][6][7]. However, C-arylation reactions have not been investigated to the same extent as other C–C bond forming reactions. A great deal