A recent overview on the synthesis of 1,4,5-trisubstituted 1,2,3-triazoles

• Pezhman Shiri,
• Ali Mohammad Amani and
• Thomas Mayer-Gall

Beilstein J. Org. Chem. 2021, 17, 1600–1628, doi:10.3762/bjoc.17.114

• at room temperature. First, several nonactivated arylalkynes containing electron-rich and electron-deficient groups as well as thiophene derivatives afforded the desired 5-arylated triazole derivatives. Then, the diversity of arylboronic acids was explored. The arylboronic acids containing some

Recent advances in palladium-catalysed asymmetric 1,4–additions of arylboronic acids to conjugated enones and chromones

• Jan Bartáček,
• Jan Svoboda,
• Martin Kocúrik,
• Jaroslav Pochobradský,
• Alexander Čegan,
• Miloš Sedlák and
• Jiří Váňa

Beilstein J. Org. Chem. 2021, 17, 1048–1085, doi:10.3762/bjoc.17.84

• Sciences, Faculty of Chemical Technology, University of Pardubice, Studentská 573, 532 10 Pardubice, Czech Republic 10.3762/bjoc.17.84 Abstract The transition metal (palladium)-catalysed asymmetric 1,4-addition of arylboronic acids to conjugated enones belong to the most important and emerging strategies

• given combination of enone and arylboronic acid. Keywords: asymmetric reaction; boronic acid; conjugated enones; chromones; enantioselective catalysis; Michael addition; Pd complexes; Introduction The asymmetric 1,4-addition of arylboronic acids to conjugated cyclic enones and chromones is a very

• -up report of the Miyaura group in 2007 provided an experimental protocol that allowed the addition of arylboronic acids instead of aryltrifluoroborates [34]. The previously used catalysts PdL1a,b were combined with additional silver salts (AgBF4 or AgSbF6) that greatly accelerated the transmetalation

Synthesis of 10-O-aryl-substituted berberine derivatives by Chan–Evans–Lam coupling and investigation of their DNA-binding properties

• Peter Jonas Wickhorst,
• Mathilda Blachnik,
• Denisa Lagumdzija and
• Heiko Ihmels

Beilstein J. Org. Chem. 2021, 17, 991–1000, doi:10.3762/bjoc.17.81

• berberrubine and berberine derivatives were synthesized by the Cu2+-catalyzed Chan–Evans–Lam coupling of berberrubine with arylboronic acids and subsequent 9-O-methylation. The reaction is likely introduced by the Cu2+-induced demethylation of berberrubine and subsequent arylation of the resulting 10-oxyanion

Helicene synthesis by Brønsted acid-catalyzed cycloaromatization in HFIP [(CF₃)₂CHOH]

• Takeshi Fujita,
• Noriaki Shoji,
• Nao Yoshikawa and
• Junji Ichikawa

Beilstein J. Org. Chem. 2021, 17, 396–403, doi:10.3762/bjoc.17.35

• ) in the teraryl structure, because the diborylated arenes were less available. Either (a) the coupling of boronic acid esters bearing one acetal moiety with dihalogenated arenes or (b) the coupling of dihalogenated arenes bearing two acetal moieties with arylboronic acids were conducted for the

¹⁹F NMR as a tool in chemical biology

• Diana Gimenez,
• Aoife Phelan,
• Cormac D. Murphy and
• Steven L. Cobb

Beilstein J. Org. Chem. 2021, 17, 293–318, doi:10.3762/bjoc.17.28

Recent progress in the synthesis of homotropane alkaloids adaline, euphococcinine and N-methyleuphococcinine

• Dimas J. P. Lima,
• Antonio E. G. Santana,
• Michael A. Birkett and
• Ricardo S. Porto

Beilstein J. Org. Chem. 2021, 17, 28–41, doi:10.3762/bjoc.17.4

• racemic, it presented a few steps and led to N-methyleuphococcinine ((±)-3) in good yields. Besides, arylboronic acids proved to be efficient catalysts for the C-allylation of unprotected oximes. Using this method, the authors accessed the racemic form of N-methyleuphococcinine (3) in 6 steps with a total

• [α]D20 −6.4 (c 0.83, MeOH); {lit. [α]D20 −6.5 (c 1.80, MeOH), [26]} for (−)-euphococcinine (2) and [α]D20 −12.6 (c 0.85, CHCl3); {lit. [α]D −13 (CHCl3), [17]} for (−)-adaline (1). Kurti synthesis – 2020 Kürti et al. developed racemic N-methyleuphococcinine ((±)-3), exploring the use of arylboronic

• acids as catalysts for C-allylation of unprotected oximes with allyl boronates [58]. After screening to find the best reaction conditions, oxime 103 was converted to α-tertiary acetal-protected hydroxylamine (±)-104 in the presence of 3,5-difluorophenylboronic acid and diisopropyl allyl boronate (108

Chan–Evans–Lam N1-(het)arylation and N1-alkеnylation of 4-fluoroalkylpyrimidin-2(1H)-ones

• Viktor M. Tkachuk,
• Oleh O. Lukianov,
• Mykhailo V. Vovk,
• Isabelle Gillaizeau and
• Volodymyr A. Sukach

Beilstein J. Org. Chem. 2020, 16, 2304–2313, doi:10.3762/bjoc.16.191

• Enamine LTD, 78 Chervonotkats‘ka str., Kyiv 02094, Ukraine 10.3762/bjoc.16.191 Abstract The Chan–Evans–Lam reaction of 1-unsubstituted 4-fluoroalkylpyrimidin-2(1Н)-ones with arylboronic acids is reported as a facile synthetic route to hitherto unavailable N1-(het)aryl and N1-alkenyl derivatives of the

• , whereas originally it required very high temperatures, and some limitations including mostly low yields and intolerance of sensitive functional groups have been partially overcome [14]. A search for new efficient reagents for copper-catalyzed N-arylation has led to the recognition of arylboronic acids as

Synthetic approaches to bowl-shaped π-conjugated sumanene and its congeners

• Shakeel Alvi and
• Rashid Ali

Beilstein J. Org. Chem. 2020, 16, 2212–2259, doi:10.3762/bjoc.16.186

• reaction as the critical step [54]. Towards this goal, they started with the hexabromination of sumanene using bromine and iron powder in nitrobenzene to provide the desired compound 94 in 61% yield. Having the bromosumanene 94 in hand, it was then subjected to the Suzuki coupling with several arylboronic

• acids in the presence of Pd(PPh3)4 and K2CO3 in THF/water to furnish the required hexaarylated sumanenes in 20–85% yields (Scheme 23). In the same year, the groups of Hisaki, Sato and Sakurai have reported a hydrogen-bonded 2D sumanene buckybowl framework having 4,4’-dicarboxy-o-terphenyl groups in the

Palladium-catalyzed regio- and stereoselective synthesis of aryl and 3-indolyl-substituted 4-methylene-3,4-dihydroisoquinolin-1(2H)-ones

• Valeria Nori,
• Antonio Arcadi,
• Armando Carlone,
• Fabio Marinelli and
• Marco Chiarini

Beilstein J. Org. Chem. 2020, 16, 1084–1091, doi:10.3762/bjoc.16.95

• (Te), Italy 10.3762/bjoc.16.95 Abstract Cascade cyclocarbopalladation of the readily available aryl/alkyl-substituted propargylic amides containing an aryl iodide moiety, followed by Suzuki–Miyaura coupling with arylboronic acids, allowed an efficient regio- and stereoselective synthesis of

• aminopalladation/reductive elimination. Keywords: alkynylanilines; arylboronic acids; indoles; isoquinolinones; palladium; Introduction The isoquinolinone nucleus is a key constituent of many natural products [1][2][3] and pharmaceuticals [4][5][6]. Substituted isoquinolinones have been found in biologically

• catalytic system showed that the ligand-free PdCl2 was the most effective catalyst (Table 1, entry 14). Other catalysts such as Pd(PPh3)4, Pd/C or Pd(OAc)2 provided inferior results (Table 1, entries 11–13). We then examined the reaction of 2a with 1.5 equiv of a variety of arylboronic acids. Using the

Synthesis and anticancer activity of bis(2-arylimidazo[1,2-a]pyridin-3-yl) selenides and diselenides: the copper-catalyzed tandem C–H selenation of 2-arylimidazo[1,2-a]pyridine with selenium

• Mio Matsumura,
• Tsutomu Takahashi,
• Hikari Yamauchi,
• Shunsuke Sakuma,
• Yukako Hayashi,
• Tadashi Hyodo,
• Tohru Obata,
• Kentaro Yamaguchi,
• Yasuyuki Fujiwara and
• Shuji Yasuike

Beilstein J. Org. Chem. 2020, 16, 1075–1083, doi:10.3762/bjoc.16.94

• successive use of imidazopyridine, Se powder, and aryl donors were developed in 2018 as more convenient methods for the synthesis of 3-selanylimidazopyridines. Guo, Li, et al. reacted imidazopyridines, Se powder, and arylboronic acids in the presence of Ag2CO3 (2 equiv) and Cs2CO3 (2 equiv) using a CuI/1,10

Copper-based fluorinated reagents for the synthesis of CF₂R-containing molecules (R ≠ F)

• Louise Ruyet and
• Tatiana Besset

Beilstein J. Org. Chem. 2020, 16, 1051–1065, doi:10.3762/bjoc.16.92

• pentafluoroethylating reagents Several research groups investigated the generation of a CuCF2CF3 species from different fluorinated precursors offering various technological solutions. In 2014, a study from Mikami reported the functionalization of a panel of (hetero)arylboronic acids (10 examples, up to 95% yield) and

• (Phen)2Cu(O2CCF2RF) and functionalization of (hetero)aryl iodides. Pentafluoroethylation of arylboronic acids and (hetero)aryl bromides via the in situ-generated CuCF2CF3 species from ethyl pentafluoropropionate and CuCl. aYields were determined by 19F NMR using benzotrifluoride (BTF) or

Pd-catalyzed asymmetric Suzuki–Miyaura coupling reactions for the synthesis of chiral biaryl compounds with a large steric substituent at the 2-position

• Yongsu Li,
• Bendu Pan,
• Xuefeng He,
• Wang Xia,
• Yaqi Zhang,
• Hao Liang,
• Chitreddy V. Subba Reddy,
• Rihui Cao and
• Liqin Qiu

Beilstein J. Org. Chem. 2020, 16, 966–973, doi:10.3762/bjoc.16.85

• compounds can be obtained in excellent yields and good enantioselectivities under mild conditions, by using brominated amides and arylboronic acids as substrates, as well as palladium and chiral-bridged biphenyl monophosphine ligands as catalysts. Results and Discussion 2-Bromo-3-methyl-N-phenylbenzamide

• silica gel. The enantiomeric excess value of the product was determined by HPLC by using an AD-H, OD-H or IA-3 column. (R)-MeO-MOP and our ligands. Asymmetric Suzuki–Miyaura coupling. Reaction conditions: 1 equiv N-aryl-bromoaryl compounds, 2 equiv arylboronic acids, 5 mol % Pd, 6 mol % ligand, 3 equiv

• of K3PO4, 2 mL THF, 50 ⁰C, 72 h; Yields are combined isolated values; ee values were determined by HPLC with chiral columns. Asymmetric Suzuki–Miyaura coupling. Reaction conditions: 1 equiv of bromoaryl compounds, 2 equiv of arylboronic acids, 5 mol % Pd, 6 mol % of ligand, 3 equiv of K3PO4, 2 mL THF

Recent applications of porphyrins as photocatalysts in organic synthesis: batch and continuous flow approaches

• Rodrigo Costa e Silva,
• Luely Oliveira da Silva,
• Aloisio de Andrade Bartolomeu,
• Timothy John Brocksom and
• Kleber Thiago de Oliveira

Beilstein J. Org. Chem. 2020, 16, 917–955, doi:10.3762/bjoc.16.83

• hydroxylation of arylboronic acids by a reductive quenching using a MOF Sn(IV) porphyrin-containing photocatalyst (UNLPF-12) under visible light irradiation. The authors obtained a variety of phenolic products in 83–96% yields (Scheme 15) [40]. The key steps of the mechanism are both the generation of

• synthesis of a Zr-based MOF with meso-tetrakis(4-carboxyphenyl)porphyrin (TCPP) (MOF-525, Zr6(OH)4O4(C48N4O8H26)3) [42] and showed its photocatalytic efficiency for oxidative hydroxylation of arylboronic acids [43]. The phenol products were obtained in quantitative yields for all evaluated arylboronic acids

• oxidative hydroxylation of arylboronic acids using UNLPF-12 as heterogeneous photocatalyst. Photocatalytic oxidative hydroxylation of arylboronic acids using MOF-525 as heterogeneous photocatalyst. Preparation of the heterogeneous photocatalyst CNH. Photoinduced sulfonation of alkenes with sulfinic acid

Asymmetric synthesis of CF₂-functionalized aziridines by combined strong Brønsted acid catalysis

• Xing-Fa Tan,
• Fa-Guang Zhang and
• Jun-An Ma

Beilstein J. Org. Chem. 2020, 16, 638–644, doi:10.3762/bjoc.16.60

• no enantioselectivity at all. As arylboronic acids have been harnessed to enhance the Brønsted acidity in asymmetric organocatalysis in combination with chiral diols or chiral aminoalcohols [40][41][42][43][44], we envisioned that the simultaneous use of arylboronic acids and chiral Brønsted acids

• examination on various arylboronic acids, solvent, temperature, and catalyst loadings resulted in no obvious improvement (Table 1, entries 9–15). Among them, the highest yield of 4a was observed (81%, Table 1, entry 12), albeit with slightly reduced ee value. This enhancement in catalytic activity could be

A systematic review on silica-, carbon-, and magnetic materials-supported copper species as efficient heterogeneous nanocatalysts in “click” reactions

• Pezhman Shiri and
• Jasem Aboonajmi

Beilstein J. Org. Chem. 2020, 16, 551–586, doi:10.3762/bjoc.16.52

• magnetic nanoparticles CuFe2O4@starch (131). The catalytic activity of 131 was studied in the synthesis of 1,2,3-triazoles substituted at the 1- and 4-position by regioselective “click“ reactions of benzyl/alkyl bromides or arylboronic acids, sodium azide, and aromatic/alkyl alkynes in the presence of low

Synthesis and optoelectronic properties of benzoquinone-based donor–acceptor compounds

• Daniel R. Sutherland,
• Nidhi Sharma,
• Georgina M. Rosair,
• Ifor D. W. Samuel,
• Ai-Lan Lee and
• Eli Zysman-Colman

Beilstein J. Org. Chem. 2019, 15, 2914–2921, doi:10.3762/bjoc.15.285

• arylboronic acids are readily accessible, we envisaged that our Pd-catalyzed direct C–H functionalization method would be ideal for attempting a facile and direct route to a series of novel substituted benzoquinone-based charge-transfer derivatives, with the aim of exploring their electroluminescent (EL

Recent advances in transition-metal-catalyzed incorporation of fluorine-containing groups

• Xiaowei Li,
• Xiaolin Shi,
• Xiangqian Li and
• Dayong Shi

Beilstein J. Org. Chem. 2019, 15, 2213–2270, doi:10.3762/bjoc.15.218

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

• carbonate as a base under aerobic conditions. Along with the synthesis of pyrido[1,2-a]benzimidazoles 78, they have reported the synthesis of benzimidazo[1,2-a]quinoline 79 and benzimidazo[1,2-a]isoquinoline 80 in good to excellent yields. They have used differently substituted arylboronic acids 77 as one

Synthesis of non-racemic 4-nitro-2-sulfonylbutan-1-ones via Ni(II)-catalyzed asymmetric Michael reaction of β-ketosulfones

• Alexander N. Reznikov,
• Anastasiya E. Sibiryakova,
• Marat R. Baimuratov,
• Eugene V. Golovin,
• Victor B. Rybakov and
• Yuri N. Klimochkin

Beilstein J. Org. Chem. 2019, 15, 1289–1297, doi:10.3762/bjoc.15.127

• -ligands [23]. The asymmetric addition of various nucleophiles to unsaturated sulfones is also considered as an effective route to chiral sulfones. The conjugated addition of arylboronic acids to unsaturated sulfones under catalysis of Rh complexes was reported [24][25][26]. It was shown that arylboronic

• acids are attached to 1,2-disubstituted α,β-unsaturated sulfones in the presence of the Rh/(S,S)-chiraphos catalytic system. Modern methods for the synthesis of functionalized sulfones, with stereocenters in the side chain, by Michael addition are based, mainly, on the use of vinyl sulfones as Michael

Robust perfluorophenylboronic acid-catalyzed stereoselective synthesis of 2,3-unsaturated O-, C-, N- and S-linked glycosides

• Madhu Babu Tatina,
• Xia Mengxin,
• Rao Peilin and
• Zaher M. A. Judeh

Beilstein J. Org. Chem. 2019, 15, 1275–1280, doi:10.3762/bjoc.15.125

• the reaction of 3,4,6-tri-O-acetyl-D-glucal (1a) with benzyl alcohol (2) in the presence of 20 mol % of arylboronic acids in different solvents (Table 1, entries 1–6). Phenylboronic acid failed to promote the reaction in several solvents and the starting glucal 1a was recovered unchanged (Table 1

Multicomponent reactions (MCRs): a useful access to the synthesis of benzo-fused γ-lactams

• Edorta Martínez de Marigorta,
• Jesús M. de Los Santos,
• Ana M. Ochoa de Retana,
• Javier Vicario and
• Francisco Palacios

Beilstein J. Org. Chem. 2019, 15, 1065–1085, doi:10.3762/bjoc.15.104

• 106. Oxindoles The simplest protocol for the multicomponent assembly of oxindole heterocycles is the palladium-catalysed reaction involving carbon monoxide, in addition to terminal alkynes, arylboronic acids and alkyl iodides, which has been applied to the preparation of fluorinated 3

• -diarylallylidene)oxindoles 132, respectively. Initially [114][115], using arylboronic acids 130 (R = Ar2), a variety of twenty-one diarylmethylene oxindoles 131 were obtained with good yields. When aryl iodide and arylboronic acids bearing different substituents are used, the expected stereochemistry of the

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

• , antidepressant or antileukotriene agents (Figure 1). Three of the five most selling drugs in 2015 were organosulfur compounds. The majority of methods for C–S bond synthesis use transition metal-catalyzed cross coupling of thiols and their derivatives with organohalides [4][5][6], arylboronic acids [7], aryl

Synergistic approach to polycycles through Suzuki–Miyaura cross coupling and metathesis as key steps

• Sambasivarao Kotha,
• Milind Meshram and
• Chandravathi Chakkapalli

Beilstein J. Org. Chem. 2018, 14, 2468–2481, doi:10.3762/bjoc.14.223

• , Suzuki coupling of 79 with diverse arylboronic acids (e.g., phenylboronic acid (36)) gave a highly substituted naphthoxepine derivative 80 (90%) (Scheme 12). Stilbene derivatives Hoveyda and co-workers [44] reported the synthesis of Z-(pinacolato)allylboron and Z-(pinacolato)alkenylboron derivatives via

Synthesis of indolo[1,2-c]quinazolines from 2-alkynylaniline derivatives through Pd-catalyzed indole formation/cyclization with N,N-dimethylformamide dimethyl acetal

• Antonio Arcadi,
• Sandro Cacchi,
• Giancarlo Fabrizi,
• Francesca Ghirga,
• Antonella Goggiamani,
• Antonia Iazzetti and
• Fabio Marinelli

Beilstein J. Org. Chem. 2018, 14, 2411–2417, doi:10.3762/bjoc.14.218

• or by sequential Pd-catalyzed reaction of o-(o-aminophenylethynyl)aniline with DMFDMA. Keywords: arylboronic acids; DMFDMA; indoles; indoloquinazolines; quinazolines; Introduction Indoloquinazoline derivatives constitute an important class of compounds which exhibit a wide range of biological

• )anilines 15 (see below). Results and Discussion We have previously reported that arylboronic acids 12 can be used in place of aryl halides in the Pd-catalyzed synthesis of indoles through aminopalladation/reductive elimination reaction from 2-alkynyltrifluoroacetanilides [24]. This reaction is carried out

• acids 12, are summarized in Table 1. In some cases, 12-unsubstituted indolo[1,2-c]quinazoline derivatives 13 were also obtained as byproducts. Electron-rich arylboronic acids worked quite well (Table 1, entries 1, 3, and 4). However, an attempt to carry out the reaction under air, instead of under O2

Some mechanistic aspects regarding the Suzuki–Miyaura reaction between selected ortho-substituted phenylboronic acids and 3,4,5-tribromo-2,6-dimethylpyridine

• Piotr Pomarański,
• Piotr Roszkowski,
• Jan K. Maurin,
• Armand Budzianowski and
• Zbigniew Czarnocki

Beilstein J. Org. Chem. 2018, 14, 2384–2393, doi:10.3762/bjoc.14.214

• compounds. The opposite selectivity using differently ortho-substituted phenylboronic acids was observed. Both electron-poor and electron-rich arylboronic acids were successfully employed. These results may be helpful in the construction of chiral atropisomeric derivatives of arylpyridine. Structures of