Comparison of crystal structure and DFT calculations of triferrocenyl trithiophosphite’s conformance

• Ruslan P. Shekurov,
• Mikhail N. Khrizanforov,
• Ilya A. Bezkishko,
• Tatiana P. Gerasimova,
• Almaz A. Zagidullin,
• Daut R. Islamov and
• Vasili A. Miluykov

Beilstein J. Org. Chem. 2022, 18, 1499–1504, doi:10.3762/bjoc.18.157

• properties. Such switchable systems with conjugated organic fragments containing an FeII/FeIII system were used in organic electronics as molecular switches, optoelectronic materials and in biochemistry as photonic or redox devices [6]. A promising approach is the coordination self-assembly of multiferrocene

Microelectrode arrays, electrosynthesis, and the optimization of signaling on an inert, stable surface

• Kendra Drayton-White,
• Siyue Liu,
• Yu-Chia Chang,
• Sakashi Uppal and
• Kevin D. Moeller

Beilstein J. Org. Chem. 2022, 18, 1488–1498, doi:10.3762/bjoc.18.156

• associated electrodes resulting in a change in the ability of the electrode to either oxidize or reduce the group. This causes a change in the current measured for the redox reaction [14]. Alternatively, the binding event can be detected with an indirect, impedance-based method. This method works by

• inserting a functionalized electrode into a solution containing a redox mediator. The mediator is oxidized at the electrodes in the array and reduced at a remote counter electrode. This results in a current that can be measured at each electrode in the array. The protein target is then added to the solution

• functionalized electrode into a solution containing a redox mediator and then monitoring the current associated with a redox mediator. The method is different relevant to the traditional methods lacking the polymer surface in that the current is dependent on changes to the polymer coating; a situation that can

Naphthalimide-phenothiazine dyads: effect of conformational flexibility and matching of the energy of the charge-transfer state and the localized triplet excited state on the thermally activated delayed fluorescence

• Kaiyue Ye,
• Liyuan Cao,
• Davita M. E. van Raamsdonk,
• Zhijia Wang,
• Jianzhang Zhao,
• Daniel Escudero and
• Denis Jacquemin

Beilstein J. Org. Chem. 2022, 18, 1435–1453, doi:10.3762/bjoc.18.149

• NI-PTZ dyads, and the synthesis route is mentioned in the following section of molecular design and structural confirmation. These dyads are different from the previously reported dyads by the substitution position, and the number of PTZ moieties attached on the NI unit, as well as the redox

• originating from the peri-H atoms on the two chromophores. We also tuned the redox potentials by oxidation of the electron donor PTZ (NI-PTZ-O). Thus, the energy of CT states and the matching with their 3LE counterpart can be altered. We underline that the approach of oxidation of the PTZ unit, which has

• redshift of the CT absorption band (centered at 405 nm) as compared to that of 3-phenyl NI [43]. These results show that our methods for tuning the electronic coupling between the donor and acceptor groups by alternation of the redox potentials of the donor (or acceptor), variation of the distance between

Synthesis and electrochemical properties of 3,4,5-tris(chlorophenyl)-1,2-diphosphaferrocenes

• Almaz A. Zagidullin,
• Farida F. Akhmatkhanova,
• Mikhail N. Khrizanforov,
• Robert R. Fayzullin,
• Tatiana P. Gerasimova,
• Ilya A. Bezkishko and
• Vasili A. Miluykov

Beilstein J. Org. Chem. 2022, 18, 1338–1345, doi:10.3762/bjoc.18.139

• )phosphonium bromides 6. Synthesis of 3,4,5-tris(chlorophenyl)-1,2-diphosphacyclopentadienides 7 and 3,4,5-tris(chlorophenyl)-1,2-diphosphaferrocenes 8. Electrochemical data for the redox properties of 3,4,5-triaryl-1,2-diphosphaferrocenes 8b and 8c. Supporting Information Supporting Information File 290

A one-pot electrochemical synthesis of 2-aminothiazoles from active methylene ketones and thioureas mediated by NH₄I

• Shang-Feng Yang,
• Pei Li,
• Zi-Lin Fang,
• Sen Liang,
• Hong-Yu Tian,
• Bao-Guo Sun,
• Kun Xu and
• Cheng-Chu Zeng

Beilstein J. Org. Chem. 2022, 18, 1249–1255, doi:10.3762/bjoc.18.130

• and Life, Beijing University of Technology, Beijing 100124, China 10.3762/bjoc.18.130 Abstract The electrochemical preparation of 2-aminothiazoles has been achieved by the reaction of active methylene ketones with thioureas assisted by ᴅʟ-alanine using NH4I as a redox mediator. The electrochemical

Polymer and small molecule mechanochemistry: closer than ever

• José G. Hernández

Beilstein J. Org. Chem. 2022, 18, 1225–1235, doi:10.3762/bjoc.18.128

• polymerizations [57][58][59], arylations and borylations [60], trifluoromethylations [61], as well as dehydrogenative couplings and cycloadditions [62], among others [63][64] in which mechanically polarized piezoelectric materials triggered redox chemistry. Alternative strategies to transduce mechanical force to

• effective to mechanically polarize redox active mechanophores such as piezoelectric materials, for which the activation in solid state by ball milling is becoming more frequent. Therefore, despite the apparent differences between both methodological approaches, which is partially attributed to the ability

Derivatives of benzo-1,4-thiazine-3-carboxylic acid and the corresponding amino acid conjugates

• Péter Kisszékelyi,
• Tibor Peňaška,
• Klára Stankovianska,
• Mária Mečiarová and
• Radovan Šebesta

Beilstein J. Org. Chem. 2022, 18, 1195–1202, doi:10.3762/bjoc.18.124

• transform into a green-blue chromophore in the presence of peroxides or redox-active metal ions under acidic conditions, creating a potential detection method for such entities [29]. Additionally, the same structure was used for the preparation of a benzo-1,4-thiazine-based cyanine chromophore, which showed

Reductive opening of a cyclopropane ring in the Ni(II) coordination environment: a route to functionalized dehydroalanine and cysteine derivatives

• Oleg A. Levitskiy,
• Olga I. Aglamazova,
• Yuri K. Grishin and
• Tatiana V. Magdesieva

Beilstein J. Org. Chem. 2022, 18, 1166–1176, doi:10.3762/bjoc.18.121

• construction of complex multifunctional molecules [3][4][5][6][7][8]. Recently, we elaborated a versatile electrochemical approach for the stereoselective functionalization of a side chain of amino acids involved in the Ni(II) chiral coordination environment [9][10][11][12][13][14][15]. A combination of redox

• -activity and chirality provided by the Ni–Schiff base template, supported with the protection from redox-destruction of the amino acid skeleton, makes the suggested approach a convenient route to various types of non-proteinogenic amino acids [9][10][12][13]. Recently, several practical approaches to α,α

• moiety may be expected to be more prone to the ring opening, and the irreversibility of the cathodic redox process observed in the voltammograms (Epc = −1.60 V vs Ag/AgCl, KCl(sat.) for 3 and Epc = −1.50 V for 4; Figure 1) supported the suggestion. In the reverse anodic scan, a new oxidation peak (A in

Electro-conversion of cumene into acetophenone using boron-doped diamond electrodes

• Mana Kitano,
• Tsuyoshi Saitoh,
• Shigeru Nishiyama,
• Yasuaki Einaga and
• Takashi Yamamoto

Beilstein J. Org. Chem. 2022, 18, 1154–1158, doi:10.3762/bjoc.18.119

• /or cathode. Boron-doped diamond (BDD) is a relatively new electrode material [15][16] and shows a wide potential window, which can be applied to the transformation of compounds with high redox potentials. Therefore, BDD electrodes would enable a straightforward oxidation reaction of aromatic alkyls

Enzymes in biosynthesis

• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2022, 18, 1131–1132, doi:10.3762/bjoc.18.116

• , requiring a sophisticated enzymology [4]. Recent developments show us that there is still much more to discover, e.g., altemicidin was shown to be enzymatically constructed from NAD+ and SAM that usually serve as enzyme cosubstrates in redox transformations and methylations but are rarely used to construct

A Streptomyces P450 enzyme dimerizes isoflavones from plants

• Run-Zhou Liu,
• Shanchong Chen and
• Lihan Zhang

Beilstein J. Org. Chem. 2022, 18, 1107–1115, doi:10.3762/bjoc.18.113

• trace amount of 3 was detected by HRMS analysis (Figure S8, Supporting Information File 1). Redox partners might be responsible for the different regioselectivity between in vivo and in vitro reactions, as it has been reported that different reductases would lead to different diastereomeric dimers of

Radical cation Diels–Alder reactions of arylidene cycloalkanes

• Kaii Nakayama,
• Hidehiro Kamiya and
• Yohei Okada

Beilstein J. Org. Chem. 2022, 18, 1100–1106, doi:10.3762/bjoc.18.112

• , single-electron oxidation of an electron-rich dienophile generates its radical cation which is then trapped by the diene (Figure 1). Since the forming cyclohexene remains in the radical cation state as well, one electron reduction is required to complete the net redox neutral transformation. Therefore, a

Electrochemical formal homocoupling of sec-alcohols

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

Beilstein J. Org. Chem. 2022, 18, 1062–1069, doi:10.3762/bjoc.18.108

• ]. Electroorganic chemistry has been recognized as an environmentally benign and powerful strategy to promote redox reactions using electricity as a traceless oxidant or reductant [24][25][26][27][28]. Electrochemical pinacol coupling would be a promising alternative to avoid the use of low-valent metal reductants

Synthesis, optical and electrochemical properties of (D–π)₂-type and (D–π)₂Ph-type fluorescent dyes

• Kosuke Takemura,
• Kazuki Ohira,
• Taiki Higashino,
• Keiichi Imato and
• Yousuke Ooyama

Beilstein J. Org. Chem. 2022, 18, 1047–1054, doi:10.3762/bjoc.18.106

• band, but also intense fluorescence emission both in solution and the solid state. Keywords: (D–π)2 structure; fluorescence; fluorescent dyes; photoabsorption; redox properties; Introduction The design and development of a new type of organic fluorescent dyes have been of considerable scientific and

Electrochemical vicinal oxyazidation of α-arylvinyl acetates

• Yi-Lun Li,
• Zhaojiang Shi,
• Tao Shen and
• Ke-Yin Ye

Beilstein J. Org. Chem. 2022, 18, 1026–1031, doi:10.3762/bjoc.18.103

• have reported a manganese dioxide-catalyzed radical azidation of enol acetates to afford the corresponding azidoketones using dioxygen as the oxidant (Scheme 1A) [14]. The adoption of electrosynthesis in green and sustainable redox transformations has been experiencing a dynamic renaissance [15][16][17

Isolation and biosynthesis of daturamycins from Streptomyces sp. KIB-H1544

• Yin Chen,
• Jinqiu Ren,
• Ruimin Yang,
• Jie Li,
• Sheng-Xiong Huang and
• Yijun Yan

Beilstein J. Org. Chem. 2022, 18, 1009–1016, doi:10.3762/bjoc.18.101

• . Diarylcyclopentenones, characteristic constituents of mushrooms [23], were rarely discovered in Streptomyces species. These components exhibit redox activity and are involved in reducing ferric (Fe3+) in the Fenton-based biological decomposition of lignocellulose [24][25]. The biosynthetic pathway of p-terphenyl was

First example of organocatalysis by cathodic N-heterocyclic carbene generation and accumulation using a divided electrochemical flow cell

• Daniele Rocco,
• Ana A. Folgueiras-Amador,
• Richard C. D. Brown and
• Marta Feroci

Beilstein J. Org. Chem. 2022, 18, 979–990, doi:10.3762/bjoc.18.98

• replaces toxic chemical redox reagents and dangerous procedures [22][23][24][25]. At present, electrosynthesis in batch is more widely used and reported in literature, but some disadvantages can be encountered: the need for high concentrations of supporting electrolyte, poor performance for synthesis such

• improved by 10%, but the yield of 2b increased only 2% (Table 2, entry 3). However, in these experiments methyl ester 3a was isolated (24% yield) as byproduct derived from methanol, which passed through the membrane, reacting with the Breslow intermediate through a redox neutral process (Scheme 5) [19]. We

• with the isopropyl alcohol the formation of the ester was only 37%, probably due to steric hindrance. In two cases (Table 3, entries 1 and 2) oxidation byproducts (esters 4a and 4b) were obtained, where the olefinic double bond is preserved. In contrast to the internal redox reactions of cinnamaldehyde

Electrochemical and spectroscopic properties of twisted dibenzo[g,p]chrysene derivatives

• Tomoya Imai,
• Ryuhei Akasaka,
• Naruhiro Yoshida,
• Toru Amaya and
• Tetsuo Iwasawa

Beilstein J. Org. Chem. 2022, 18, 963–971, doi:10.3762/bjoc.18.96

• voltammogram of DBC-H exhibited a reversible, two-step, two-electron redox process, with Eox1 and Eox2 values of 0.34 V and 0.72 V, respectively (Figure 2a). The value of Eox1 is 0.06 V lower than that of MeO-DBC-1 which does not contain isopropyl groups. This is in contrast to MeO-DBC-3, in which four MeO

• DBC-SMe showed a reversible two-electron redox process, with Eox1 and Eox2 values of 0.41 V and 0.88 V, respectively (Figure 2c) [53]. It is interesting to note that DBC-SMe exhibited a higher oxidation potential than DBC-H despite the electron-donating nature due to mesomeric effects based on lone

• pairs of sulfur atoms. In the CV of DBC-Br, a one-electron redox was observed as a reversible process, but a second redox process was not observed (Figure 2d). On the other hand, both the first and second oxidation processes were observed in the SWV of DBC-Br (Eox1 and Eox2 are 0.79 V and 1.15 V

Introducing a new 7-ring fused diindenone-dithieno[3,2-b:2',3'-d]thiophene unit as a promising component for organic semiconductor materials

• Valentin H. K. Fell,
• Joseph Cameron,
• Alexander L. Kanibolotsky,
• Eman J. Hussien and
• Peter J. Skabara

Beilstein J. Org. Chem. 2022, 18, 944–955, doi:10.3762/bjoc.18.94

• compound, EtH-T-DI-DTT, consisting of seven, fused ring systems, with an electron-rich central DTT core, flanked by electron-withdrawing keto groups. Absorption studies in solution and in the solid state show strong aggregation of the molecules in films. EtH-T-DI-DTT shows excellent redox stability with

Cathodic generation of reactive (phenylthio)difluoromethyl species and its reactions: mechanistic aspects and synthetic applications

• Sadanobu Iwase,
• Shinsuke Inagi and
• Toshio Fuchigami

Beilstein J. Org. Chem. 2022, 18, 872–880, doi:10.3762/bjoc.18.88

• are shown in Figure 1. As shown in Figure 1b, a typical reversible redox couple (E1/2red = −1.69 V vs. SSCE) of o-phthalonitrile was clearly observed. A significantly enhanced cathodic peak current was observed after addition of compound 1 to the solution containing o-phthalonitrile while the anodic

• place. Thus, it was found that o-phthalonitrile should work as an electron transfer catalyst, i.e., a redox mediator. On the bases of the cyclic voltammetric measurements, the cathodic reduction of 1 was carried out at a constant potential using o-phthalonitrile as mediator. As shown in Scheme 5, the

Synthesis of α-(perfluoroalkylsulfonyl)propiophenones: a new set of reagents for the light-mediated perfluoroalkylation of aromatics

• Durbis J. Castillo-Pazos,
• Juan D. Lasso and
• Chao-Jun Li

Beilstein J. Org. Chem. 2022, 18, 788–795, doi:10.3762/bjoc.18.79

• synthetic chemistry, we report the synthesis of a series of bench-stable α-(perfluoroalkylsulfonyl)propiophenones. Their application as photocleavable reagents was tested with electron-rich aromatics under metal-free, redox- and pH-neutral conditions to enable late-stage perfluorooctylation

• halogenation reactions or oxidation. For these reasons, it would be ideal to develop an efficient methodology that allows for the generation of perfluoroalkyl radicals in a mild, redox- and pH-neutral manner, without the assistance of external photocatalysts, heavy metal catalysts, or further additives. Thus

• , the expansion of our previously reported propiophenone family of reagents was envisioned as suitable alternative to produce a bench stable, organic soluble, and iodine-free perfluroalkylation source. In 2017, our group developed a metal-free and redox-neutral protocol for the photoinduced alkylation

Menadione: a platform and a target to valuable compounds synthesis

• Acácio S. de Souza,
• Ruan Carlos B. Ribeiro,
• Dora C. S. Costa,
• Fernanda P. Pauli,
• David R. Pinho,
• Matheus G. de Moraes,
• Fernando de C. da Silva,
• Luana da S. M. Forezi and
• Vitor F. Ferreira

Beilstein J. Org. Chem. 2022, 18, 381–419, doi:10.3762/bjoc.18.43

• shown a wide range of biological activities of menadione, such as anticancer [15][16][17][18][19][20][21][22], antibacterial [23][24][25][26], antifungal [27][28], antimalarial [29][30][31][32], antichagasic [33], and anthelmintic [34] effects. In these cases, the redox cycle of menadione, followed by

• , followed by oxidation, thus establishing a redox cycle. The main characteristics of the quinones (Q) redox cycle, comprises the one-electron reduction to generate a semiquinone intermediate (SQ) and the two-electron reduction leading to hydroquinone (HQ), in NAD(P)H oxidase-dependent processes [35][36][37

• •−), hydrogen peroxide (H2O2), hydroxyl radical (•OH), and hydroperoxyl radical (•OOH) (Figure 3) [35]. Additionally, the menadione semiquinone radical can participate in another redox cycle, such as, the Fenton reaction, also resulting in the production of hydroxyl and hydroperoxyl radicals (Figure 3) [39][40

Earth-abundant 3d transition metals on the rise in catalysis

• Nikolaos Kaplaneris and
• Lutz Ackermann

Beilstein J. Org. Chem. 2022, 18, 86–88, doi:10.3762/bjoc.18.8

• underdeveloped. This lack of viable catalysis strategies involving 3d transition metals is largely due to a limited knowledge on the working mode of these metal catalysts, which often involve single-electron-transfer-based redox events. As a consequence, there is a strong demand for efficient and reliable

1,2-Naphthoquinone-4-sulfonic acid salts in organic synthesis

• Ruan Carlos B. Ribeiro,
• Patricia G. Ferreira,
• Amanda de A. Borges,
• Luana da S. M. Forezi,
• Fernando de Carvalho da Silva and
• Vitor F. Ferreira

Beilstein J. Org. Chem. 2022, 18, 53–69, doi:10.3762/bjoc.18.5

• electrons through a redox cycle promoted by the 1,2- or 1,4-naphthoquinone system. In this cycle, transient reactive oxygen (ROS) and nitrogen (RNS) species are formed as free radicals, peroxides, superoxide anions, radical anions, or dianions. These species generated inside cells accelerate hypoxia and

• addition to the sulfonic acid substitution reaction of position C4 of β-NQS, quinone can be involved in a redox process and, therefore, can be used as an electrode in electrochemical processes. Subsequently, Legua and co-workers [56][57] applied this method to determine amphetamines in urine. Figure 3

• cleaner and form the substitution product at position C4. Fieser and Fieser were the first to study tautomerism between 4-arylamino-1,2-naphthoquinone A and 2-hydroxy-1,4-naphthoquinone-4-arylimine B (Scheme 3C) using the redox potential compared to the pH of the medium. It was observed that

Recent advances and perspectives in ruthenium-catalyzed cyanation reactions

• Thaipparambil Aneeja,
• Cheriya Mukkolakkal Abdulla Afsina,
• Padinjare Veetil Saranya and
• Gopinathan Anilkumar

Beilstein J. Org. Chem. 2022, 18, 37–52, doi:10.3762/bjoc.18.4

• metal. Ruthenium complexes have astonishing characteristics such as high electron transfer ability, low redox potentials, high Lewis acidity, and greater stabilities of the reactive metallic species like oxometals, metallacycles, and metal carbene complexes [27]. The wide availability of highly reactive