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

•  24) [52]. A one-pot and multicomponent protocol for the synthesis of 5-selanyltriazoles 85 from the reaction of ethynylstibanes 82, organic azides 83, and diaryl diselenides 84 using catalytic amounts of CuI and 1,10-phenanthroline in DMSO at 60 °C under air with good to high yield was presented by

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

• excellent in almost every example (Table 35) [14][15]. Selected addition products were used as intermediates in the total syntheses of various biologically active compounds (Scheme 24) [14][15][16]. Catalytic systems based on different groups of ligands The use of the chiral 1,10-phenanthroline ligand L15

Synthetic accesses to biguanide compounds

• Oleksandr Grytsai,
• Cyril Ronco and
• Rachid Benhida

Beilstein J. Org. Chem. 2021, 17, 1001–1040, doi:10.3762/bjoc.17.82

• -phenanthroline in refluxing DMF as an optimal catalytic system, the formation of the biguanide intermediate proceeded cleanly, followed by N-arylation to provide a series of N1-aryl heptasubstituted biguanides in gratifying 63–81% yield (Scheme 41). Interestingly, Štrukil et al. reported that the use of two

Microwave-assisted multicomponent reactions in heterocyclic chemistry and mechanistic aspects

• Shivani Gulati,
• Stephy Elza John and
• Nagula Shankaraiah

Beilstein J. Org. Chem. 2021, 17, 819–865, doi:10.3762/bjoc.17.71

• . One such demonstration was reported by Padmini and co-workers [64] wherein a four-component reaction between substituted aldehydes 5, phenanthroline (63), malononitrile (51) and isocyanides 21 afforded pyrrolo[1,10]-phenanthrolines 64 in ethanol as a solvent with excellent yields. The conventional

• phenanthroline. 6 Pyrimidines/fused pyrimidines 6.1 Pyrimidines Pyrimidines are six-membered aromatic heterocycles containing two nitrogen atoms at positions 1 and 3. These are an important class of compounds depicting a wide range of biological activities such as COX inhibitors, anti-inflammatory, anticancer

Using multiple self-sorting for switching functions in discrete multicomponent systems

• Amit Ghosh and
• Michael Schmittel

Beilstein J. Org. Chem. 2020, 16, 2831–2853, doi:10.3762/bjoc.16.233

• from [Cu(25)]+ and translocated to the free phenanthroline sites of the deck 27. The ensuing complex [Cu3(27)]3+ now commanded the nanoslider 26•29 to dismantle and to transfer the biped 29 thus enabling the formation of the alternative device [Cu3(27)(29)]3+. In essence, a single input (Zn2+) was

• the concurrent generation of [Cu2(28)(31)]2+, with the latter complex representing a three-component nanorotor operating at 46 kHz at room temperature (state SelfSORT-II). In [Cu2(28)(31)]2+ the rotator 28 exchanged rapidly between the two peripheral copper(I) phenanthroline sites of 31. Importantly

• between the states was accomplished by the addition of twice 2-ferrocenyl-1,10-phenanthroline (69) followed by the addition of copper(I) ions (Figure 19). In the state SelfSORT-I, representing an incomplete self-sorted mixture of ten components, piperidine (70) was firmly bound at the zinc porphyrin

Synthesis and investigation of quadruplex-DNA-binding, 9-O-substituted berberine derivatives

• Jonas Becher,
• Daria V. Berdnikova,
• Heiko Ihmels and
• Christopher Stremmel

Beilstein J. Org. Chem. 2020, 16, 2795–2806, doi:10.3762/bjoc.16.230

• a lower affinity [38]. Along the same line, the influence of the length and substituents of the side chains at the G4-DNA ligands have been assessed for quinolinium [43], indoloquinoline [44][45], phenanthroline [46], phenothiazine [47], and thiazole orange [48] derivatives. In these studies, the

Catalytic trifluoromethylation of iodoarenes by use of 2-trifluoromethylated benzimidazoline as trifluoromethylating reagent

• Tatsuhiro Uchikura,
• Nanami Kamiyama,
• Taisuke Ishikawa and
• Takahiko Akiyama

Beilstein J. Org. Chem. 2020, 16, 2442–2447, doi:10.3762/bjoc.16.198

• -withdrawing (–CF3, 4g) groups furnished 3a in low yields. Moreover, other electron-withdrawing ligands, i.e., phenanthroline derivatives (4h and 4i), and electron-donating ligands such as 2,2’-biimidazole (4j) and tetramethylethylenediamine (4k) gave inferior results. We next screened for the generality of

Oxime radicals: generation, properties and application in organic synthesis

• Igor B. Krylov,
• Stanislav A. Paveliev,
• Alexander S. Budnikov and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2020, 16, 1234–1276, doi:10.3762/bjoc.16.107

• that the presence of 1,10-phenanthroline is necessary to stabilize the intermediate CuCF3. Aromatic oximes with various electron-donating and electron-withdrawing substituents afford cyclization products in high yields (products 147a–d). In addition to aryl oximes, benzyl and tert-butyl substituted

• aliphatic amine ligands (N,N,N′,N′-tetramethylethylenediamine and 1,1,4,7,10,10-hexamethyltriethylenetetramine) showed moderate results and aromatic nitrogen-containing ligands (2,2’-bipyridine and phenanthroline) were even less efficient for the synthesis of target the isoxazolines. Both aromatic (products

Activated carbon as catalyst support: precursors, preparation, modification and characterization

• Melanie Iwanow,
• Tobias Gärtner,
• Volker Sieber and
• Burkhard König

Beilstein J. Org. Chem. 2020, 16, 1188–1202, doi:10.3762/bjoc.16.104

• et al. demonstrated the preparation of carbon materials with high surface areas from protic ionic liquids and salts. The precursors have low-molecular weights, are available and cheap. Preparation of the carbon materials is simple: Neutralization of the nitrogen-containing bases, e.g., phenanthroline

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

• anticancer activity are described. The double C–H selenation of imidazo[1,2-a]pyridine with Se powder was catalyzed by CuI (10 mol %) ligated with 1,10-phenanthroline (10 mol %) at 130 °C under aerobic conditions. The selenides or diselenides were prepared almost selectively using selenium powder in an

• -phenanthroline catalytic system [28]. Guo, Han, et al. reported a method that used a Cu(OAc)2/1,10-phenanthroline catalyst in the presence of KOH (2 equiv); this method replaced the aryl source from an arylboronic acid with an aryl iodide [30]. Zhou et al. reported the reactions of imidazopyridines, Se powder

• , and aryl halides in the presence of Na2CO3 (2 equiv) using a NiBr2/2,2-bipyridine system [31]. We also developed reactions of imidazopyridines, Se powder, and triarylbismuthanes using a CuI/1,10-phenanthroline catalytic system that did not require a base or an additive [32]. On the other hand, the

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

• ) and 1,10-phenanthroline as a ligand was crucial in their system. In 2012, Prakash also studied the in situ generation of CuCF2H from n-Bu3SnCF2H, the presence of DMF being the key to stabilize the CuCF2H intermediate [41] (Scheme 2). From these seminal works, a handful of reports was then published by

• -generated copper-based reagent (19 examples, up to 80% yield, Scheme 7e). With a similar method and in the presence of 1,10-phenanthroline as a ligand, the functionalization of alkenyl halides (8 examples, up to 82% yield), allyl halides (7 examples, up to 99% yield) and benzyl bromides (6 examples, up to

• reagents for perfluoroalkylation reactions [66], Hartwig developed in 2011 the (Phen)CuCF3 and (Phen)CuCF2CF2CF3 complexes from inexpensive reagents. Indeed, when mixing (CuOt-Bu)4, 1,10-phenanthroline and the corresponding TMSRF, the perfluoroalkyl copper complexes were isolated for the first time (Scheme

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

• triazole products, excellent reusability, short reaction times, and good to high yields. Further, Dufauda et al. reported a copper(II)–phenanthroline complex supported on the SBA-15 architecture, Cu(II)phen@SBA-15 (58) [31]. The preparation is outlined in Scheme 9: Initially, phen-functionalized mesoporous

Controlling alkyne reactivity by means of a copper-catalyzed radical reaction system for the synthesis of functionalized quaternary carbons

• Goki Hirata,
• Yu Yamane,
• Naoya Tsubaki,
• Reina Hara and
• Takashi Nishikata

Beilstein J. Org. Chem. 2020, 16, 502–508, doi:10.3762/bjoc.16.45

• with good regio- and stereoselectivity. Results and Discussion In our preliminary research, we tried various Cu salts, including CuI, CuBr, CuCl, CuOAc, and CuOTf, and ligands, including PPh3, 1,10-phenanthroline (1,10-Phen), N,N,N',N'',N''-pentamethyldiethylenetriamine, and tris(2-pyridylmethyl)amine

Recent advances in photocatalyzed reactions using well-defined copper(I) complexes

• Mingbing Zhong,
• Xavier Pannecoucke,
• Philippe Jubault and
• Thomas Poisson

Beilstein J. Org. Chem. 2020, 16, 451–481, doi:10.3762/bjoc.16.42

• bisnitrogen ligands, and particularly phenanthroline derivatives, were used in the pioneering reports from McMillin [14] and Sauvage [15]. For decades, their use in organic synthesis, and particularly catalysis, has been ignored. However, since 2012, a renewed interest toward their use in catalysis has been

• chlorotrifluoromethylated product (Scheme 3). In 2019, Bissember and co-workers reported the synthesis of new homoleptic copper complexes by modifying the structure of the phenanthroline ligand at the 1- and 10-positions with various aromatic substituents [19]. These complexes were fully characterized and evaluated in a

• phenanthroline derivative and a bisisonitrile ligand, [Cu(I)(dpp)(binc)]BF4, which was fully characterized (Scheme 15) [32]. This complex proved to have a similar or higher excited state lifetime (17 μs) compared to the previously reported complexes and a redox potential of −1.88 V vs SCE in the excited state

Six-fold C–H borylation of hexa-peri-hexabenzocoronene

• Mai Nagase,
• Kenta Kato,
• Akiko Yagi,
• Yasutomo Segawa and
• Kenichiro Itami

Beilstein J. Org. Chem. 2020, 16, 391–397, doi:10.3762/bjoc.16.37

• borylation of unsubstituted HBC. HBC was pulverized by a ball mill prior to use. First, we attempted the iridium catalyst and reagents that we have reported as the suitable C–H borylation conditions for warped nanographene: [Ir(OMe)cod]2, 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen), HBpin (Bpin: 4,4,5,5

• stirring bar was added HBC (10.0 mg, 19.1 μmol, 1.0 equiv). The flask was put in an argon-filled glove box, and a solution of [Ir(OMe)cod]2 (1.9 mg, 2.9 μmol, 15 mol %) and 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen; 1.4 mg, 5.9 μmol, 31 mol %) in a dry solvent (300 μL) was added to the flask. Then

Photoreversible stretching of a BAPTA chelator marshalling Ca²⁺-binding in aqueous media

• Aurélien Ducrot,
• Arnaud Tron,
• Robin Bofinger,
• Ingrid Sanz Beguer,
• Jean-Luc Pozzo and
• Nathan D. McClenaghan

Beilstein J. Org. Chem. 2019, 15, 2801–2811, doi:10.3762/bjoc.15.273

• spectrofluorometer fitted with a PMT detector and exciting with a 450 W Xe lamp across a double monochromator, and were corrected for instrumental response. Photoreaction quantum yields were determined upon excitation at 365 nm using the couple potassium ferrioxalate–phenanthroline as a chemical actinometer on an

Photochromic diarylethene ligands featuring 2-(imidazol-2-yl)pyridine coordination site and their iron(II) complexes

• Andrey G. Lvov,
• Max Mörtel,
• Anton V. Yadykov,
• Frank W. Heinemann,
• Valerii Z. Shirinian and
• Marat M. Khusniyarov

Beilstein J. Org. Chem. 2019, 15, 2428–2437, doi:10.3762/bjoc.15.235

• ligand systems, including 1,10-phenanthroline, 2-(azol-2-yl)pyridine, and related frameworks to yield photochromic ligands. The latter can be divided into two groups based on the position of the metal coordination site relative to the photoactive hexatriene unit of a diarylethene. Some diarylethene-based

• , resulted in the hypsochromic shift of long-wavelength absorption band, which could be due to keto–enol tautomerization in the ethene bridge [43]. Overall, the thermal stabilities of the new ligands are comparable to those of phenanthroline-based photochromic ligand I [19]. Synthesis and structure of iron

• synthesized. All ligands show good combinations of cyclization/cycloreversion quantum yields, whereas the thermal stability of closed-ring isomers is comparable with those reported for a diarylethene-based ligand with a phenanthroline bridge. Cyclohexenone ligand 6 readily forms a dimeric complex 8 with “FeII

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

• phenanthroline derivative. This complex was applied to the SN2 fluorination of primary and secondary alkyl bromides, producing the corresponding alkyl fluorides in 40–90% yield (Scheme 26). In 2014, the group of Lalic [69] developed a mild fluorination of alkyl triflates with potassium fluoride catalyzed by a

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 9-O-arylated berberines via copper-catalyzed C_Ar–O coupling reactions

• Qiaoqiao Teng,
• Xinhui Zhu,
• Qianqian Guo,
• Weihua Jiang,
• Jiang Liu and
• Qi Meng

Beilstein J. Org. Chem. 2019, 15, 1575–1580, doi:10.3762/bjoc.15.161

• -alkylated BBR, the synthesis of 9-O-phenyl BBR 3a was initially attempted by direct cross-coupling of berberrubine (BBRB) with phenyl iodide, using CuI and 1,10-phenanthroline as the pre-catalyst and K2CO3 as the base [18][19]. However, under these reaction conditions not any desired product was formed, and

Complexation of a guanidinium-modified calixarene with diverse dyes and investigation of the corresponding photophysical response

• Yu-Ying Wang,
• Yong Kong,
• Zhe Zheng,
• Wen-Chao Geng,
• Zi-Yi Zhao,
• Hongwei Sun and
• Dong-Sheng Guo

Beilstein J. Org. Chem. 2019, 15, 1394–1406, doi:10.3762/bjoc.15.139

• photophysical behavior of Ru(II) complexes affected by calixarenes has been studied by different groups. Kirsch-De Mesmaeker and co-workers reported that the luminescence of [Ru(TAP)2(phen)]2+ (TAP = 1,4,5,8-tetraazaphenanthrene, phen = 1,10-phenanthroline) complex could be quenched by the phenol moieties of a

Selective detection of DABCO using a supramolecular interconversion as fluorescence reporter

• Indrajit Paul,
• Debabrata Samanta,
• Sudhakar Gaikwad and
• Michael Schmittel

Beilstein J. Org. Chem. 2019, 15, 1371–1378, doi:10.3762/bjoc.15.137

• equipped with a trimethoxyphenyl group to furnish a fourth coordination to the copper(I) center and a sterically crowded duryl group to prevent homoleptic complexation, while lutidine 9 was selected to strengthen the HETPYP-I [33] (HETeroleptic PYridine and Phenanthroline complexation) coordination. In

• this setting, the binary complex 12 = [(4)(10)2] and the heteroleptic metal complex 11 = [Cu(8)(9)]+ quantitatively formed side by side in a two-fold completive self-sorting. Lutidine 9 has a higher binding preference towards the copper phenanthroline [Cu(8)]+ (log K(9)·[Cu(8)]+ = 4.60 ± 0.21

• phenanthroline and very similar to the one experienced by the methyl protons (f2’-H) that are diagnostically shifted upfield to −0.63 ppm. Proton h-H is equally split into two sets reflecting the strong coordination of one methoxy group at an unsymmetrically coordinated copper(I) center. Similar to model system

Synthesis of aryl cyclopropyl sulfides through copper-promoted S-cyclopropylation of thiophenols using cyclopropylboronic acid

• Emeline Benoit,
• Ahmed Fnaiche and
• Alexandre Gagnon

Beilstein J. Org. Chem. 2019, 15, 1162–1171, doi:10.3762/bjoc.15.113

• the solvent for toluene, dichloromethane, dimethylformamide or DMF/H2O (4:1) led to lower yields of the desired aryl cyclopropyl sulfide 1a (Table 1, entry 5) while decreasing the temperature to 50 °C almost completely shut down the reaction (Table 1, entry 6). 1,10-Phenanthroline was found to be the

• (II) acetate, 0.1 equivalents of 1,10-phenanthroline, 2.0 equivalents of potassium carbonate under oxygen atmosphere at 70 °C for 20 hours in a 3:1 mixture of toluene and water afforded the aryl cyclopropyl sulfide 1a in 38% along with 8% of the corresponding side-product 26a and 24% of recovered

Mechanochemistry of supramolecules

• Anima Bose and
• Prasenjit Mal

Beilstein J. Org. Chem. 2019, 15, 881–900, doi:10.3762/bjoc.15.86

• appropriate metal ion(s) and ligand(s) has been demonstrated in various reports [46][47][48][49]. In Figure 1, a comprehensive framework is shown in which nanoscale architectures are built from various monodentate (pyridine; Figure 1a), bidentate (bipyridine, phenanthroline; Figure 1b) and tridentate

Organometallic vs organic photoredox catalysts for photocuring reactions in the visible region

• Aude-Héloise Bonardi,
• Frédéric Dumur,
• Guillaume Noirbent,
• Jacques Lalevée and
• Didier Gigmes

Beilstein J. Org. Chem. 2018, 14, 3025–3046, doi:10.3762/bjoc.14.282

• )-complexes have been widely used. For example, bis(1,10-phenanthroline)copper(I) (abbreviated Cu(phen)22+) is reported in ref [37] as an efficient photoredox catalyst for ATRP upon a simple household blue LED. Ir-based photoredox catalyst are also efficient in this mechanism such as tris(2-phenylpyridinato