Synthesis of meso-pyrrole-substituted corroles by condensation of 1,9-diformyldipyrromethanes with pyrrole

• Baris Temelli and
• Pinar Kapci

Beilstein J. Org. Chem. 2022, 18, 1403–1409, doi:10.3762/bjoc.18.145

• porphyrins, are tetrapyrrolic aromatic compounds, with the lack of one meso-carbon atom on the macrocycle [1][2][3][4]. This feature supplies a smaller ring cavity than in the case of porphyrins, three NH in the core, and coordination ability with high-valence transition metal ions. It is noteworthy that

Synthesis of C6-modified mannose 1-phosphates and evaluation of derived sugar nucleotides against GDP-mannose dehydrogenase

• Sanaz Ahmadipour,
• Alice J. C. Wahart,
• Jonathan P. Dolan,
• Laura Beswick,
• Chris S. Hawes,
• Robert A. Field and
• Gavin J. Miller

Beilstein J. Org. Chem. 2022, 18, 1379–1384, doi:10.3762/bjoc.18.142

• Asp260 & Asp109 in coordination with Mg2+ and two water molecules in close proximity to C6 [16]. Evaluation of GDP 6-chloro-6-deoxy-ᴅ-mannose against GMD GMD from P. aeruginosa was co-incubated with GDP-mannose 1 and sugar nucleotide 19, and the production of NADH monitored by fluorescence (excitation

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

• objects of growing interest in the fields of coordination chemistry [3][4][5] and asymmetric catalysis [6][7]. Due to the sp2-hybridization of the phosphorus atom, phosphaferrocenes are commonly regarded as phosphorus ligands with weaker σ-donor character than classical tertiary phosphines and stronger π

• mediator in the synthesis of asymmetric phosphines starting from white phosphorus [15]. Moreover, the presence of the lone pair of the P atom opens the route to polynuclear complexes [16][17][18] and coordination polymers [19][20][21] with the mixed σ-/π-coordination mode, which is not typical for

Make or break: the thermodynamic equilibrium of polyphosphate kinase-catalysed reactions

• Michael Keppler,
• Sandra Moser,
• Henning J. Jessen,
• Christoph Held and
• Jennifer N. Andexer

Beilstein J. Org. Chem. 2022, 18, 1278–1288, doi:10.3762/bjoc.18.134

• fractions [5][10][15][16]. Based on the crystal structures of three PPK2-III, the coordination of polyP and ADP by positively charged amino acids (lysine and arginine) has been suggested [16][17]. Two magnesium ions are held in place by two conserved aspartate residues that further coordinate the polyP and

• [33][34]. Under physiological conditions as well as in an in vitro system the actual ΔG may be different by coordination of cations and the ionic strength, temperature and pH of the reaction solution [29][35][36]. Compared to other ATP synthesis reactions very little is known about the thermodynamics

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

• ) coordination environment in the form of a Schiff base is considered as a route to electrochemical broadening of the donor–acceptor cyclopropane concept in combination with chirality induction in the targeted products. A tendency to the reductive ring-opening and the follow-up reaction paths of thus formed

• 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

• stereoselective functionalization has not been probed as yet. Herein, reductive three-membered ring opening in the chiral α,α-cyclopropanated amino acids involved in the Ni(II)–Schiff base coordination environment is reported. Follow-up transformations of thus formed radical anions will be discussed, including

Scope of tetrazolo[1,5-a]quinoxalines in CuAAC reactions for the synthesis of triazoloquinoxalines, imidazoloquinoxalines, and rhenium complexes thereof

• Laura Holzhauer,
• Chloé Liagre,
• Olaf Fuhr,
• Nicole Jung and
• Stefan Bräse

Beilstein J. Org. Chem. 2022, 18, 1088–1099, doi:10.3762/bjoc.18.111

• ). Increasing the amount of alkyne 4 increases the probability of the alkyne being coordinated in contrast to the tetrazole, which leads to launching of the CuAAC cycle. The probability of coordination on the tetrazole should also be indirectly impacted by this. However, the imidazole formation is only slightly

• -triazoloquinoxaline ligand in a distorted octahedral coordination geometry in all cases. The obtained data for the alkyl-chain complex 27a corresponds to similar published results [12]. For complex 29, single crystals were formed from slow evaporation of a methylene chloride solution under ambient conditions. The

• crystal structure confirmed that rhenium is coordinated to three carbonyl groups, the bromine atom and two nitrogens of the 1,2,3-triazoloquinoxaline ligand. However, in this case, instead of coordination via the quinoxaline nitrogen and the 2-nitrogen of the triazole ring, the complex is formed via

Post-synthesis from Lewis acid–base interaction: an alternative way to generate light and harvest triplet excitons

• Hengjia Liu and
• Guohua Xie

Beilstein J. Org. Chem. 2022, 18, 825–836, doi:10.3762/bjoc.18.83

• materials with the introduction of Lewis acids have been frequently observed due to either physical or chemical interactions. In this mini-review, we elaborate how Lewis acids adjust the optical properties and the bandgap of luminescent materials by simple coordination reactions. It is common that

• fluorescent materials containing Lewis basic nitrogen heterocycles are more likely to provide the feasible band gap modulation. The essence of such phenomenon originates from Lewis acid–base coordination and adducts, which highly depends on the electron-accepting property of the Lewis acids. This

• coordination between Lewis acids and bases, which can finely adjust the optoelectronic properties of the fluorescent molecules, such as band gaps, peak wavelengths, and even frontier molecular orbitals if bound together [20]. The traditional way to manipulate the optoelectronic properties of the emitters

Identification of the new prenyltransferase Ubi-297 from marine bacteria and elucidation of its substrate specificity

• Jamshid Amiri Moghaddam,
• Huijuan Guo,
• Karsten Willing,
• Thomas Wichard and
• Christine Beemelmanns

Beilstein J. Org. Chem. 2022, 18, 722–731, doi:10.3762/bjoc.18.72

• tyrosine (Tyr-56) residue, which likely fulfills a similar coordinative function. Furthermore, a conserved arginine residue (UbiA-297 R145) was detectable, which was located in the neighboring α-helix (R145) and in proximity to the binding motif, and was hypothesized to be involved in the coordination

Structural basis for endoperoxide-forming oxygenases

• Takahiro Mori and
• Ikuro Abe

Beilstein J. Org. Chem. 2022, 18, 707–721, doi:10.3762/bjoc.18.71

• ) [64][65][66][67]. The Fe(II) is coordinated by the conserved 2-His-1-Asp residues and a 2OG in the active site. The binding of a substrate in the active site, where it is close to the Fe(II) center, provides a coordination site for O2. Subsequently, the oxidative decarboxylation of 2OG generates a

• bond interactions. Grey dashed lines show the coordination of the iron atom. Iron atoms are depicted by orange spheres. Structure of NvfI [28]. (A–C) Conformational changes of loop regions: (A) open conformation, (B) partially closed conformation, and (C) closed conformation of NvfI. (D) The active

Heteroleptic metallosupramolecular aggregates/complexation for supramolecular catalysis

• Prodip Howlader and
• Michael Schmittel

Beilstein J. Org. Chem. 2022, 18, 597–630, doi:10.3762/bjoc.18.62

• and size of their cavity requires often tedious de-novo synthesis. Eventually, these drawbacks have been tackled by synthesizing discrete supramolecular hosts based on metal–ligand coordination-driven self-assembly [15][16][17][18][19][20][21][22][52]. This approach not only solved the issue with low

• overall yields, but it also provided chemists with a superior control over the shape and size of the host’s cavity. Since the coordination bonds which define the host structure are labile in nature, they allow the formation of thermodynamically controlled architectures using a self-correcting mechanism

• solvents restricts their use in potential applications. In this aspect, coordination-driven discrete architectures provide a promising future due to their facile one-pot synthesis and high solubility in common solvents. Mukherjee and co-workers have developed supramolecular architectures containing

BINOL as a chiral element in mechanically interlocked molecules

• Matthias Krajnc and
• Jochen Niemeyer

Beilstein J. Org. Chem. 2022, 18, 508–523, doi:10.3762/bjoc.18.53

• characteristic for the diphenylphenanthroline units (281 and 337 nm). This indicates a chiral coordination geometry around the Cu ion, most probably brought about by a non-perpendicular orientation of the phenanthrolines. Thus, the axially chiral BINOL units induce a chiral, helical geometry for the Cu complex

Synthesis of 3,4,5-trisubstituted isoxazoles in water via a [3 + 2]-cycloaddition of nitrile oxides and 1,3-diketones, β-ketoesters, or β-ketoamides

• Md Imran Hossain,
• Md Imdadul H. Khan,
• Seong Jong Kim and
• Hoang V. Le

Beilstein J. Org. Chem. 2022, 18, 446–458, doi:10.3762/bjoc.18.47

• chlorides to form furoxans also known as 1,2,5-oxadiazole 2-oxides, a class of structures with important biological activities due to their unique electronic nature and coordination ability. Keywords: environmentally friendly; furoxans; 1,2,5-oxadiazole 2-oxides; trifluoromethyl-substituted isoxazoles

• donors have shown important biological activities due to their unique electronic and coordination ability [37][38], such as antitumor [39] and antiparasitic [40][41]. Previously, furoxans were synthesized via dimerization of hydroximoyl chlorides in the presence of a base, such as trimethylamine in ether

• activities due to their unique electronic and coordination ability. Experimental General information All chemicals and solvents were obtained from Sigma-Aldrich or Fisher Scientific and were used as received unless specified. 1H NMR and 13C NMR spectra were recorded on a Bruker-400 and or a Bruker-500

Tetraphenylethylene-embedded pillar[5]arene-based orthogonal self-assembly for efficient photocatalysis in water

• Zhihang Bai,
• Krishnasamy Velmurugan,
• Xueqi Tian,
• Minzan Zuo,
• Kaiya Wang and
• Xiao-Yu Hu

Beilstein J. Org. Chem. 2022, 18, 429–437, doi:10.3762/bjoc.18.45

• tunable self-assembly, such as vesicles [14][15][16], micelles [17][18][19], nanocrystals [20], coordination-driven assemblies [9][21][22], host–guest interactions [15][23][24][25], etc. In the above systems, catalysts are encapsulated by supramolecular assemblies and thus provide a suitable environment

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

• ]. Chang’s group reported the use of 3D crystalline polyoxometalate-based coordination polymers (POMCPs) as heterogeneous catalysts, with H2O2, to synthesize 10 and the best result was obtained using H[CuII(ttb)(H2O)3]2[CuII(ttb)Cl]2[PW12O40]·4H2O (Httb = 1-(tetrazol-5-yl)-4-(triazol-1-yl)benzene) as the

Amamistatins isolated from Nocardia altamirensis

• Till Steinmetz,
• Wolf Hiller and
• Markus Nett

Beilstein J. Org. Chem. 2022, 18, 360–367, doi:10.3762/bjoc.18.40

• function. Due to the similarity of both molecules, we propose that compound 6 possesses the same absolute configuration as pseudomonin A. The affinities of compound 1–6 for the coordination of ferric iron were evaluated with the CAS assay [9] and compared with EDTA [13]. While the half-maximal displacement

Unexpected chiral vicinal tetrasubstituted diamines via borylcopper-mediated homocoupling of isatin imines

• Marco Manenti,
• Leonardo Lo Presti,
• Giorgio Molteni and
• Alessandra Silvani

Beilstein J. Org. Chem. 2022, 18, 303–308, doi:10.3762/bjoc.18.34

• Scheme 2, which likely starts from the catalytic generation, in our experimental conditions, of the borylcopper(II) species A. Such copper complex proved to be not isolable, but could be easily generated in situ and may act as a genuine Cu(II) catalyst, with a labile coordination site [30]. According to

Iridium-catalyzed hydroacylation reactions of C1-substituted oxabenzonorbornadienes with salicylaldehyde: an experimental and computational study

• Angel Ho,
• Austin Pounder,
• Krish Valluru,
• Leanne D. Chen and
• William Tam

Beilstein J. Org. Chem. 2022, 18, 251–261, doi:10.3762/bjoc.18.30

• its derivatives were used in all calculations rather than the experimentally used precatalyst [Ir(COD)Cl]2, as ligand exchange with the hydroxide ions present likely generates the [Ir(COD)OH]2 species in solution. Upon monomerization of [Ir(COD)OH]2, either through solvolysis or coordination of the

• substrate, the active catalyst Ir(COD)OH will undergo oxidative addition into the aldehyde C–H bond. Next, the iridium hydride species will undergo exo-η2-coordination with the olefin of MeOBD to generate intermediates IN1a and IN1b (Figure 1). It is typically assumed exo-η2-coordination is preferential

• over endo-η2-coordination, as the less congested convex face would impose reduced steric requirements. There are two potential isomeric intermediates following η2-coordination to the exo-face of MeOBD concerning the relative orientation of the COD ligand, acyl group, and C1-substituent on the

Synthesis of novel [1,2,4]triazolo[1,5-b][1,2,4,5]tetrazines and investigation of their fungistatic activity

• Anna V. Korotina,
• Svetlana G. Tolshchina,
• Rashida I. Ishmetova,
• Natalya P. Evstigneeva,
• Natalya A. Gerasimova,
• Natalya V. Zilberberg,
• Nikolay V. Kungurov,
• Gennady L. Rusinov,
• Oleg N. Chupakhin and
• Valery N. Charushin

Beilstein J. Org. Chem. 2022, 18, 243–250, doi:10.3762/bjoc.18.29

• as high-energy materials [23][24][25], molecules with promising photophysical, electrochemical and coordination properties for use in sensors, OLEDs, semiconductor materials, etc. [26][27][28]. The most important biomedical application of 1,2,4,5-tetrazines are bioorthogonal reactions that allow

Diametric calix[6]arene-based phosphine gold(I) cavitands

• Gabriele Giovanardi,
• Andrea Secchi,
• Arturo Arduini and
• Gianpiero Cera

Beilstein J. Org. Chem. 2022, 18, 190–196, doi:10.3762/bjoc.18.21

• ]. This occurs via strong steric interactions, often outside the macrocycle (Figure 1a) [11], that affect the first coordination sphere of the metal or by creating a spatial confinement around the metal that is thus directed towards the inner cavity (Figure 1b) [26][27]. Contrarily, calix[6]arene

Asymmetric organocatalytic Michael addition of cyclopentane-1,2-dione to alkylidene oxindole

• Estelle Silm,
• Ivar Järving and
• Tõnis Kanger

Beilstein J. Org. Chem. 2022, 18, 167–173, doi:10.3762/bjoc.18.18

• -protecting group and electron-withdrawing properties of the protection groups are essential for coordination with the catalyst and for the reactivity of the Michael acceptor. Using a tosyl-protected oxindole the reaction was sluggish, the yield was low and the enantioselectivity could not be determined

• ). When instead of a benzylidene-containing substrate an alkylidene with an extra ester moiety was used, the enantioselectivity was lost and the product 3i was obtained as a racemic mixture. Either additional coordination with the catalyst or a lack of π–π-interaction may have been responsible for that

Green synthesis of C5–C6-unsubstituted 1,4-DHP scaffolds using an efficient Ni–chitosan nanocatalyst under ultrasonic conditions

• Soumyadip Basu,
• Sauvik Chatterjee,
• Suman Ray,
• Suvendu Maity,
• Prasanta Ghosh,
• Asim Bhaumik and
• Chhanda Mukhopadhyay

Beilstein J. Org. Chem. 2022, 18, 133–142, doi:10.3762/bjoc.18.14

• , we synthesized a Ni–chitosan complex and exploited the coordination properties of the complex to use it as an effective and recyclable catalyst towards the green synthesis of C5–C6-unsubstituted 1,4-dihydropyridine (1,4-DHP) scaffolds. Ultrasonic irradiation is an important technique in the toolbox

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

• I which after coordination and subsequent NCTS insertion is transformed to intermadiate II. β-Elimination finally delivers the required product (Scheme 14). Later, Deb and co-workers developed a methodology towards the synthesis of N-(2-cyanoaryl)-7-azaindoles using [RuCl2(p-cymene)]2/AgOTf/NaOAc as

DABCO-promoted photocatalytic C–H functionalization of aldehydes

• Bruno Maia da Silva Santos,
• Mariana dos Santos Dupim,
• Cauê Paula de Souza,
• Thiago Messias Cardozo and
• Fernanda Gadini Finelli

Beilstein J. Org. Chem. 2021, 17, 2959–2967, doi:10.3762/bjoc.17.205

• is reduced by the photocatalyst (PC−) after coordination to aryl bromide, promoting the turnover of organometallic and photoredox cycles. DABCO is regenerated via deprotonation by an inorganic base. We also investigated the mechanism operating when the reaction is performed in the absence of bicyclic

Study on the interactions between melamine-cored Schiff bases with cucurbit[n]urils of different sizes and its application in detecting silver ions

• Jun-Xian Gou,
• Yang Luo,
• Xi-Nan Yang,
• Wei Zhang,
• Ji-Hong Lu,
• Zhu Tao and
• Xin Xiao

Beilstein J. Org. Chem. 2021, 17, 2950–2958, doi:10.3762/bjoc.17.204

• , are formed by polymerization of glycoluril, which contains rigid cavities for the study of host–guest chemistry and carbonyl groups for the study of coordination chemistry [16][17][18][19][20]. For the special methyl cucurbit[n]urils with abundant methyl groups, its high density of the

• Schiff base reaction and the nucleophilic reaction of haloalkane (Scheme 1 and Supporting Information File 1, Scheme S1) [25]. In addition to retaining the abundant coordination sites of Schiff bases, TBT is also modified with carbon chains of appropriate length for inducing host–guest interactions and

• coordination ability to metals. In this study, Q[7]-TBT was selected as a UV detector to detect common metals. As shown in Figure 5, the additional Ag+ increases the absorbance of the Q[7]-TBT complex from 0.441 to 0.555 at λmax = 258 nm, while other metal ions do not increase or decrease the absorbance

Iron-catalyzed domino coupling reactions of π-systems

• Austin Pounder and
• William Tam

Beilstein J. Org. Chem. 2021, 17, 2848–2893, doi:10.3762/bjoc.17.196

• borylmetallation across the alkene in a syn-fashion 58. Side-on coordination of the haloalkene’s π-bond can trigger a syn-carbometallation 59. A base-mediated 1,2- elimination will deliver the alkenylboration product as well as regenerate 56. The methodology was applied towards the synthesis of (±)-imperanene