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

• molecules (but also inorganic precursors, organometallic complexes, enzymes, monomeric units, or even polymers) in bulk and to provide the energy required for the system to react (Figure 1b and Figure 1c) [7][8][9][10][11][12]. At times, the methodological differences between both approaches seem to have

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

• confirmed via single crystal X-ray crystallography. Several other byproducts, such as the bistriazolo product were isolated (see Supporting Information File 1). The obtained triazoloquinoxaline and TIQ products are promising ligands for complexation with different metals. The formation of organometallic

• complexes is a well-established method to obtain interesting materials for catalysis [31][32][33] and optoelectronics [34][35], as well as for biological applications [36][37]. Therefore, the obtained triazole and TIQ products were employed to act as ligands in rhenium tricarbonyl complexes. These are

Recent advances in the asymmetric phosphoric acid-catalyzed synthesis of axially chiral compounds

• Alemayehu Gashaw Woldegiorgis and
• Xufeng Lin

Beilstein J. Org. Chem. 2021, 17, 2729–2764, doi:10.3762/bjoc.17.185

• ., fredericamycin A and acutumine [99]), SPINOL-based ligands and catalysts [100], and organometallic complexes with important applications. The use of chiral catalysts for spirocyclization reactions brings asymmetry at the site of the spirocyclic center while tolerating different electronic and steric functional

Chemical syntheses and salient features of azulene-containing homo- and copolymers

• Vijayendra S. Shetti

Beilstein J. Org. Chem. 2021, 17, 2164–2185, doi:10.3762/bjoc.17.139

• aqueous acid solution. Further, the coordination of polymers 37 and 39 to a multinuclear Ru cluster was investigated by the same group [32]. The organometallic complexes 40–43 were synthesized by treating polymers 37 and 39 with Ru3(CO)12 in refluxing xylene (Scheme 9). The ruthenium content in these

Structural effects of meso-halogenation on porphyrins

• Keith J. Flanagan,
• Maximilian Paradiz Dominguez,
• Zoi Melissari,
• Hans-Georg Eckhardt,
• René M. Williams,
• Dáire Gibbons,
• Caroline Prior,
• Gemma M. Locke,
• Alina Meindl,
• Aoife A. Ryan and
• Mathias O. Senge

Beilstein J. Org. Chem. 2021, 17, 1149–1170, doi:10.3762/bjoc.17.88

• and combined with NSD analysis to approximate the IP and OOP distortion modes. The wB97XD functional was chosen because it has been shown to produce reliable energy minimized structures for organometallic complexes and metalloporphyrins [42][43][44]. With the first series (series 1) we looked at the

In silico rationalisation of selectivity and reactivity in Pd-catalysed C–H activation reactions

• Liwei Cao,
• Mikhail Kabeshov,
• Steven V. Ley and
• Alexei A. Lapkin

Beilstein J. Org. Chem. 2020, 16, 1465–1475, doi:10.3762/bjoc.16.122

• transition metal coordination sphere; the energy of a new M–C bond formed and the thermodynamic stability of organometallic product. With new developments in computational chemistry, mechanistic studies using density functional theory (DFT) provide valuable insights into the reactivity of organometallic

• complexes in C–H activation reactions. Along with the huge increase in computing power, this method becomes practically feasible to build model systems that provide parameters of the actual experimental systems with acceptable accuracy [16]. Recently, a predictive tool using quantum mechanics descriptors

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

• organic chemistry. Despite the impressive advances reported since the renewal of the field in 2008 [2][3][4], several issues still have to be addressed. Indeed, most of the developed reactions relied on the use of organometallic complexes of expensive noble metals, such as iridium and ruthenium [5]. Even

Architecture and synthesis of P,N-heterocyclic phosphine ligands

• Wisdom A. Munzeiwa,
• Bernard Omondi and
• Vincent O. Nyamori

Beilstein J. Org. Chem. 2020, 16, 362–383, doi:10.3762/bjoc.16.35

• block for the assembly of homo and hetero-organometallic complexes. The 3- and 4-pyridylphosphine derivatives 5 have also been successfully used as templates for assembling supramolecular structures and coordination polymers [54][59]. Halogenated ring-fused pyridine reagents can also be used to generate

Syntheses and chemical properties of β-nicotinamide riboside and its analogues and derivatives

• Mikhail V. Makarov and
• Marie E. Migaud

Beilstein J. Org. Chem. 2019, 15, 401–430, doi:10.3762/bjoc.15.36

• -dihydropyridine derivatives may be also accomplished by using catalysis with organometallic complexes [72][73][74][75][76][77][78][79] or platinum nanoparticles [80]. This recently developed approach stems from an independent field of research, which focuses on the regeneration of NAD(P)H from NAD(P)+ [81][82

Olefin metathesis catalysts embedded in β-barrel proteins: creating artificial metalloproteins for olefin metathesis

• Daniel F. Sauer,
• Johannes Schiffels,
• Takashi Hayashi,
• Ulrich Schwaneberg and
• Jun Okuda

Beilstein J. Org. Chem. 2018, 14, 2861–2871, doi:10.3762/bjoc.14.265

• enzymes is quite limited. Apart from engineering natural enzymes, the approach of connecting abiotic co-factors (such as organometallic complexes) to natural or re-engineered protein scaffolds offers an attractive combination of both, broad reaction scope of chemical transformations as well as control of

A challenging redox neutral Cp*Co(III)-catalysed alkylation of acetanilides with 3-buten-2-one: synthesis and key insights into the mechanism through DFT calculations

• Andrew Kenny,
• Alba Pisarello,
• Arron Bird,
• Paula G. Chirila,
• Alex Hamilton and
• Christopher J. Whiteoak

Beilstein J. Org. Chem. 2018, 14, 2366–2374, doi:10.3762/bjoc.14.212

• in molecules (QTAIM) analysis using Multiwfn software [28] of the two intermediate structures, identifying the relevant parameters at the bond critical points (bcp) of interest. QTAIM analysis has been used previously in the field of transition metal organometallic complexes to understand ligand

Recent advances in materials for organic light emitting diodes

• Eli Zysman-Colman

Beilstein J. Org. Chem. 2018, 14, 1944–1945, doi:10.3762/bjoc.14.168

• in design, from fluorescent compounds to phosphorescent organometallic complexes to organic thermally activated delayed fluorescence (TADF) molecules, the latter driving tremendous recent excitement within the field of organic semiconductor research. This thematic issue of the Beilstein Journal of

Enhanced quantum yields by sterically demanding aryl-substituted β-diketonate ancillary ligands

• Rebecca Pittkowski and
• Thomas Strassner

Beilstein J. Org. Chem. 2018, 14, 664–671, doi:10.3762/bjoc.14.54

• emission properties of organometallic complexes can be tuned by employing different ligand structures. For platinum(II) complexes, the influence of both cyclometalating [21][22][23][24][25][26] and auxiliary ligand [27][28][29][30][31][32] on the emission color as well as their efficiency has been

Phosphonic acid: preparation and applications

• Charlotte M. Sevrain,
• Mathieu Berchel,
• Hélène Couthon and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2017, 13, 2186–2213, doi:10.3762/bjoc.13.219

Main group mechanochemistry

• Agota A. Gečiauskaitė and
• Felipe García

Beilstein J. Org. Chem. 2017, 13, 2068–2077, doi:10.3762/bjoc.13.204

• sustainable alternatives to conventional solvent-based synthetic routes. Mechanochemistry has already been successfully applied to the synthesis of active pharmaceutical ingredients (APIs), organic compounds, metal oxides, coordination compounds and organometallic complexes. In the main group arena, examples

Mechanochemical synthesis of small organic molecules

• Tapas Kumar Achar,
• Anima Bose and
• Prasenjit Mal

Beilstein J. Org. Chem. 2017, 13, 1907–1931, doi:10.3762/bjoc.13.186

• bond formation reactions, multicomponent reactions, heterocyclic ring synthesis, synthesis of organometallic complexes and their catalytic applications, and so on. Review Mechanochemical organic synthesis Famous philosopher Aristotle’s statement “No Coopora nisi Fluida” means ‘no reaction is possible

• mechanosynthesis of organometallic complexes are shown. Ćurić and co-workers reported the first mechanochemical activation of a C–H bond of unsymmetrical azobenzene with Pd(OAc)2 [178]. The cyclopalladation process was highly regioselective and the rate of palladation was also faster than traditional solution

• ]. Mechanochemical synthesis of azacenes [169]. Mechanochemical oxidative C-P bond formation [170]. Mechanochemical C–chalcogen bond formation [171]. Solvent-free synthesis of an organometallic complex. Selective examples of mechano-synthesis of organometallic complexes. a) Halogenation reaction of Re-complexes [175

Direct estimate of the internal π-donation to the carbene centre within N-heterocyclic carbenes and related molecules

• Diego M. Andrada,
• Nicole Holzmann,
• Thomas Hamadi and
• Gernot Frenking

Beilstein J. Org. Chem. 2015, 11, 2727–2736, doi:10.3762/bjoc.11.294

• theoretical approaches can be found in the literature where natural bond orbital calculations (NBO) and energy decomposition analysis (EDA) have been applied to a broad variety of organometallic complexes [35][67][68][69][70][71][72]. Although all the procedures have proven to be a convenient way to evaluate

Copper-catalyzed arylation of alkyl halides with arylaluminum reagents

• Bijay Shrestha and
• Ramesh Giri

Beilstein J. Org. Chem. 2015, 11, 2400–2407, doi:10.3762/bjoc.11.261

• , Zn and Sn in cross-coupling, the utility of organometallic complexes of Al are limited [13][14][16][17][18][19][20][21]. In many cases, direct transmetalation of organoalanes to Pd are sluggish and require ZnCl2 or CdCl2 to facilitate reactions through sequential transmetalations [19]. In some cases

Ru complexes of Hoveyda–Grubbs type immobilized on lamellar zeolites: activity in olefin metathesis reactions

• Hynek Balcar,
• Naděžda Žilková,
• Martin Kubů,
• Michal Mazur,
• Zdeněk Bastl and
• Jiří Čejka

Beilstein J. Org. Chem. 2015, 11, 2087–2096, doi:10.3762/bjoc.11.225

• ), with large BET areas and pore volumes, proved to be very suitable supports, due to easy attachment of bulky organometallic complexes onto silica surface ensuring rapid diffusion of reactants to the active catalytic sites [5][6][7][8][9][10][11][12]. Several strategies of immobilization have been

Hexacoordinate Ru-based olefin metathesis catalysts with pH-responsive N-heterocyclic carbene (NHC) and N-donor ligands for ROMP reactions in non-aqueous, aqueous and emulsion conditions

• Shawna L. Balof,
• K. Owen Nix,
• Matthew S. Olliff,
• Sarah E. Roessler,
• Arpita Saha,
• Kevin B. Müller,
• Ulrich Behrens,
• Edward J. Valente and
• Hans-Jörg Schanz

Beilstein J. Org. Chem. 2015, 11, 1960–1972, doi:10.3762/bjoc.11.212

• from commercial sources, and they were degassed and stored in the dry-box when directly used in combination with organometallic complexes, and otherwise were used without further purification. H2ITap∙HCl, complex 8, as well as DEDAM and DAMA were synthesized according to literature procedures [61][71

A facile synthetic route to benzimidazolium salts bearing bulky aromatic N-substituents

• Gabriele Grieco,
• Olivier Blacque and
• Heinz Berke

Beilstein J. Org. Chem. 2015, 11, 1656–1666, doi:10.3762/bjoc.11.182

• : benzimidazolium salts; bulky ligands; cyclization; ligand design; N-heterocyclic carbenes (NHC); ring formation; Introduction Imidazole-based N-heterocyclic carbenes (NHCs) are stable systems serving as ancillary ligands mainly to construct organometallic complexes. These NHCs are sterically and electronically

Eosin Y-catalyzed visible-light-mediated aerobic oxidative cyclization of N,N-dimethylanilines with maleimides

• Zhongwei Liang,
• Song Xu,
• Wenyan Tian and
• Ronghua Zhang

Beilstein J. Org. Chem. 2015, 11, 425–430, doi:10.3762/bjoc.11.48

• and not sustainable. Similar to the redox properties of these organometallic complexes, some metal-free organic dyes such as Eosin Y, Rose Bengal, Fluorescein, and Methylene Blue, have shown superiority of their applications as photocatalysts, which are easy to handle, environmentally friendly

Electrocarboxylation: towards sustainable and efficient synthesis of valuable carboxylic acids

• Roman Matthessen,
• Jan Fransaer,
• Koen Binnemans and
• Dirk E. De Vos

Beilstein J. Org. Chem. 2014, 10, 2484–2500, doi:10.3762/bjoc.10.260

• increase the selectivity for the C6 product, dissolved nickel and iron redox mediators have been used [48][53][54]. The need for such organometallic complexes could be eliminated by direct electrocarboxylation on nickel or stainless steel cathode surfaces [49][50]. Substrates with an internal conjugated

• ]. These organometallic complexes have also proven their value in increasing the carboxylation efficiency of alkenes, without including a specific selectivity for the monocarboxylic acid [56]. Monocarboxylation can readily occur as a side reaction when a small amount of protons are present in the reaction

Synthesis, characterization and DNA interaction studies of new triptycene derivatives

• Sourav Chakraborty,
• Snehasish Mondal,
• Rina Kumari,
• Sourav Bhowmick,
• Prolay Das and
• Neeladri Das

Beilstein J. Org. Chem. 2014, 10, 1290–1298, doi:10.3762/bjoc.10.130

• same time does not inflict any significant damage to the DNA structure even when present as a ligand in organometallic complexes of palladium [35]. We believe triptycene could be one such compound, which can act against several metabolic pathways and yet be non-DNA damaging in nature. However, to the

Atherton–Todd reaction: mechanism, scope and applications

• Stéphanie S. Le Corre,
• Mathieu Berchel,
• Hélène Couthon-Gourvès,
• Jean-Pierre Haelters and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2014, 10, 1166–1196, doi:10.3762/bjoc.10.117

• et al. [95] reports the amination of either triaryl phosphate or dialkyl aryl phosphate catalyzed by nickel organometallic complexes. It is an additional illustration of the use of aryl phosphate, which can be readily obtained by AT reactions. Beside the use of phosphorus species as a substrate in