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

• ruthenium complexes which are efficient as catalysts elevated the scope of this metal in synthetic organic chemistry. For clarity and ease of understanding of the topic, this review is categorized into four sections: cyanation of amines, cyanation of arenes and heteroarenes, photocatalyzed cyanation, and

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

• of directly connected 4,7-polyazulenes 18–20. Synthesis of (A) tert-butyl N-(6-bromoazulen-2-yl)carbamate (27), (B) dimeric aminoazulene 29, and (C) poly[2,6-aminoazulene] 31. Synthesis of poly{1,3-bis[2-(3-alkylthienyl)]azulene} 33–38. Synthesis of polymer ruthenium complexes 40–43. Synthesis of 4,7

Valorisation of plastic waste via metal-catalysed depolymerisation

• Francesca Liguori,
• Carmen Moreno-Marrodán and
• Pierluigi Barbaro

Beilstein J. Org. Chem. 2021, 17, 589–621, doi:10.3762/bjoc.17.53

Ring-closing metathesis of prochiral oxaenediynes to racemic 4-alkenyl-2-alkynyl-3,6-dihydro-2H-pyrans

• Viola Kolaříková,
• Markéta Rybáčková,
• Martin Svoboda and
• Jaroslav Kvíčala

Beilstein J. Org. Chem. 2020, 16, 2757–2768, doi:10.3762/bjoc.16.226

• metathesis or enantioselective RCEYM reactions catalyzed by ruthenium complexes are known (Scheme 3). The only RCEYM of a system containing two triple and one double bonds has been described by Gouverneur et al., who synthesized a series of dihydrooxaphosphinines by the diastereoselective metathesis of

Heterogeneous photocatalysis in flow chemical reactors

• Christopher G. Thomson,
• Ai-Lan Lee and
• Filipe Vilela

Beilstein J. Org. Chem. 2020, 16, 1495–1549, doi:10.3762/bjoc.16.125

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

• protecting groups [12]. Later, ruthenium complexes-catalyzed alkyne–azide cycloadditions (RuAACs) regioselectively produced the opposite form of the disubstituted triazoles. Thus, a wide range of azides was reacted with diverse nonactivated terminal alkyne substrates using ruthenium complexes to generate

Chiral terpene auxiliaries V: Synthesis of new chiral γ-hydroxyphosphine oxides derived from α-pinene

• Anna Kmieciak and
• Marek P. Krzemiński

Beilstein J. Org. Chem. 2019, 15, 2493–2499, doi:10.3762/bjoc.15.242

• ligands that were obtained from readily available natural (1S)-β-pinene and (1S)-α-pinene [18]. We applied these ligands for the formation of the ruthenium complexes, which were successfully used as catalysts in asymmetric transfer hydrogenation of prochiral ketones. In continuation of our studies on the

Hoveyda–Grubbs catalysts with an N→Ru coordinate bond in a six-membered ring. Synthesis of stable, industrially scalable, highly efficient ruthenium metathesis catalysts and 2-vinylbenzylamine ligands as their precursors

• Kirill B. Polyanskii,
• Kseniia A. Alekseeva,
• Pavel V. Raspertov,
• Pavel A. Kumandin,
• Eugeniya V. Nikitina,
• Atash V. Gurbanov and
• Fedor I. Zubkov

Beilstein J. Org. Chem. 2019, 15, 769–779, doi:10.3762/bjoc.15.73

• , ring-opening metathesis polymerization – ROMP and acyclic diene metathesis – ADMET. This motivates the investigations into the development of new, efficient, stable, and highly selective catalytic systems based on ruthenium complexes. However, in reality, a limited set of commercially available

• the ruthenium centre – “the upper” one is the N-heterocyclic carbene (NHC) ligand and “the lower” one is the 2-alkoxybenzylidene ligand. These determine the principal catalytic properties of the ruthenium complexes. Many ligands were tested as the upper part in various publications, which concluded

• the target ruthenium complexes shown in Scheme 4. This transformation was carried out using known standard methods including the interaction of the indenylidene derivative 8 with 1,3-dimesityl-2-(trichloromethyl)imidazolidine (9) [47][48][49][50]. Several approaches have been described earlier for the

Aqueous olefin metathesis: recent developments and applications

• Valerio Sabatino and
• Thomas R. Ward

Beilstein J. Org. Chem. 2019, 15, 445–468, doi:10.3762/bjoc.15.39

• ammonium tags Classical metathesis catalysts such as G-II and HG-II are among the most active, stable and versatile ruthenium complexes. Despite their high activity and remarkable stability, they are sparingly soluble in neat water, thus challenging their use as homogeneous catalysts in pure water. To

• significantly improve the water solubility and facilitate the removal of ruthenium residues from reaction mixtures [52][59]. The majority of such ruthenium complexes can easily be removed, especially for the metathesis of water-insoluble substrates, as demonstrated by Grela and co-workers for the RCM of

Application of olefin metathesis in the synthesis of functionalized polyhedral oligomeric silsesquioxanes (POSS) and POSS-containing polymeric materials

• Patrycja Żak and
• Cezary Pietraszuk

Beilstein J. Org. Chem. 2019, 15, 310–332, doi:10.3762/bjoc.15.28

• the properties and applications of the resulting materials. Vinylsilanes show a specific reactivity towards alkylidene ruthenium complexes because of a strong effect of the silyl group on the properties of the double bond. In general, the substituents at the silicon atom determine the regioselectivity

• of the process to a certain degree. The reactivity of vinylsilanes with different substituents at silicon towards alkylidene ruthenium complexes is illustrated in Scheme 1 [7]. According to Scheme 1a, as a result of the reaction of trialkoxy-, tris(trimethylsiloxy)-, trichloro- or dichloromethyl

• with some porosity [27]. Czaban-Jóźwiak and Grela have studied the metathetic transformation of allyl-substituted cubic silsesquioxane [28]. In search for the optimum catalyst a variety of ruthenium complexes were tested in the CM of allylsilsesquioxane with tert-butyl acrylate and (Z)-1,4-diacetoxybut

Ruthenium-based olefin metathesis catalysts with monodentate unsymmetrical NHC ligands

• Veronica Paradiso,
• Chiara Costabile and
• Fabia Grisi

Beilstein J. Org. Chem. 2018, 14, 3122–3149, doi:10.3762/bjoc.14.292

• Veronica Paradiso Chiara Costabile Fabia Grisi Dipartimento di Chimica e Biologia “Adolfo Zambelli”, Università di Salerno, Via Giovanni Paolo II 132, I-84084 Fisciano, Salerno, Italy 10.3762/bjoc.14.292 Abstract An overview on the catalytic properties of ruthenium complexes for olefin metathesis

• influencing the reactivity and selectivity of the resulting catalysts by creating different steric and/or electronic environments around the metal center. Indeed, ruthenium complexes coordinated with this kind of ligands can be easily tailored for challenging or specific metathesis applications in which their

• description of the catalytic behavior of ruthenium complexes bearing monodentate five-membered uNHCs. A special focus is given to the more recent advancements in the development of such unsymmetrical architectures for targeted metathesis applications. Ruthenium complexes with NHCs presenting alternative

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

• cycles can be observed with Ru(bpy)3. Other ruthenium complexes which can be used into photocatalytical cycles have been described in the literature and more particularly with other type of ligands. Modification of the ligands has an influence on the redox potentials and the lifetime of the excited

The influence of the cationic carbenes on the initiation kinetics of ruthenium-based metathesis catalysts; a DFT study

• Magdalena Jawiczuk,
• Angelika Janaszkiewicz and
• Bartosz Trzaskowski

Beilstein J. Org. Chem. 2018, 14, 2872–2880, doi:10.3762/bjoc.14.266

• directly to the imidazole core [28]. Finally, in the same year Ganter described a triazoliumylidene with the formal +1 charge incorporated into the five-membered ring [29]. Several complexes formed by these carbenes have been also described, however, no ruthenium complexes with such carbenes have been

• -Ind and 1–3-Hov have initiation Gibbs free energy values in the range of standard metathesis catalysts, like GrI, Ind and Hoveyda–Grubbs and are likely an interesting alternative for them. On the other hand ruthenium complexes with two carbenes are predicted to have relatively high initiation energies

• very accurate, single-point DLPNO-CCSD(T) calculations using the DFT-optimized geometries and the def2-svp basis set using Orca v4.0.0.1 program [70][71]. Complete DLPNO-CCSD(T) results are presented in Supporting Information File 1. NHC’s and their ruthenium complexes studied in this work; L = carbene

Synthesis of dihydroquinazolines from 2-aminobenzylamine: N³-aryl derivatives with electron-withdrawing groups

• Nadia Gruber,
• Jimena E. Díaz and
• Liliana R. Orelli

Beilstein J. Org. Chem. 2018, 14, 2510–2519, doi:10.3762/bjoc.14.227

• , some ruthenium complexes bearing a 3,4-dihydroquinazoline ligand have been studied as hydrogenation-transfer catalysts, showing good to excellent activity for the reduction of ketones [17]. In the context of our research on heterocyclic amidine N-oxides [18][19][20][21][22], we recently prepared some

Synthesis and photophysical studies of a multivalent photoreactive Ru^II-calix[4]arene complex bearing RGD-containing cyclopentapeptides

• Sofia Kajouj,
• Lionel Marcelis,
• Alice Mattiuzzi,
• Adrien Grassin,
• Damien Dufour,
• Pierre Van Antwerpen,
• Didier Boturyn,
• Eric Defrancq,
• Mathieu Surin,
• Julien De Winter,
• Pascal Gerbaux,
• Ivan Jabin and
• Cécile Moucheron

Beilstein J. Org. Chem. 2018, 14, 1758–1768, doi:10.3762/bjoc.14.150

• internal cell environment or exert a photocytotoxic activity. The use of lipophilic ligands allows the corresponding ruthenium complexes to passively diffuse inside cells but limits their structural and photophysical properties. Moreover, this strategy does not provide any cell selectivity. This limitation

Synthesis and supramolecular properties of regioisomers of mononaphthylallyl derivatives of γ-cyclodextrin

• Markéta Bláhová,
• Sergey K. Filippov,
• Lubomír Kováčik,
• Jiří Horský,
• Simona Hybelbauerová,
• Zdenka Syrová,
• Tomáš Křížek and
• Jindřich Jindřich

Beilstein J. Org. Chem. 2017, 13, 2509–2520, doi:10.3762/bjoc.13.248

• starting material. After the deprotection, a substantial amount of the pure γ-CD was isolated as the only byproduct containing CD. Apparently, a concurrent reaction – the cleavage of allyl ether – also took place. The use of similar ruthenium complexes as catalysts for the cleavage of allyl ethers and

Synthesis and properties of fluorescent 4′-azulenyl-functionalized 2,2′:6′,2″-terpyridines

• Adrian E. Ion,
• Liliana Cristian,
• Mariana Voicescu,
• Masroor Bangesh,
• Augustin M. Madalan,
• Daniela Bala,
• Constantin Mihailciuc and
• Simona Nica

Beilstein J. Org. Chem. 2016, 12, 1812–1825, doi:10.3762/bjoc.12.171

• by comparison with analogues ruthenium complexes with unsubstituted or 4′-phenyl-substituted terpyridine. In this contribution we report on the green synthesis and physicochemical investigations of the 4′-azulenyl-substituted terpyridines with particular interest on the fluorescence properties. The

Cp₂TiCl/D₂O/Mn, a formidable reagent for the deuteration of organic compounds

• Antonio Rosales and
• Ignacio Rodríguez-García

Beilstein J. Org. Chem. 2016, 12, 1585–1589, doi:10.3762/bjoc.12.154

• C–H bonds [8][9]. More recently, organometallic catalysts have been used in the development of methods for deuteration of organic compounds. In this sense, it has been reported that iridium complexes can catalyse the H/D exchange of arenes, cyclic alkenes and vinyl groups [10][11][12]. Ruthenium

• complexes catalyse α-deuteration of amines and alcohols [13] and palladium complexes catalyse the ortho-selective deuteration of arenes [14]. Also, SmI2/D2O-mediated the chemoselective synthesis of α,α-dideuterio alcohols directly from carboxylic acid under single-electron-transfer conditions [15]. However

Stereodynamic tetrahydrobiisoindole “NU-BIPHEP(O)”s: functionalization, rotational barriers and non-covalent interactions

• Golo Storch,
• Sebastian Pallmann,
• Frank Rominger and
• Oliver Trapp

Beilstein J. Org. Chem. 2016, 12, 1453–1458, doi:10.3762/bjoc.12.141

• Mikami reported the stereochemical alignment of BIPHEP ligands in ruthenium complexes upon addition of chiral diamine co-ligands [1][2]. The resulting complexes were successfully employed in enantioselective ketone hydrogenation. Further examples of such systems are BIPHEP complexes of rhodium [3][4][5

Chiral cyclopentadienylruthenium sulfoxide catalysts for asymmetric redox bicycloisomerization

• Barry M. Trost,
• Michael C. Ryan and
• Meera Rao

Beilstein J. Org. Chem. 2016, 12, 1136–1152, doi:10.3762/bjoc.12.110

• tertiary carbocation is trapped by a gold carbenoid intermediate to form the fused cyclopropane. While there had been reports of utilizing chiral ruthenium complexes for asymmetric catalysis prior to our studies [30][31][32][33][34][35][36][37][38][39][40], there had previously been no reported examples of

• that, upon coordination to ruthenium, create diastereomeric, chiral-at-ruthenium complexes (Figure 1c). It was unclear a priori whether this transfer of stereochemical information would have an adventitious, negligible, or detrimental impact on the enantioselectivity of the reaction. With this

The aminoindanol core as a key scaffold in bifunctional organocatalysts

• Isaac G. Sonsona,
• Eugenia Marqués-López and
• Raquel P. Herrera

Beilstein J. Org. Chem. 2016, 12, 505–523, doi:10.3762/bjoc.12.50

• disulfides and sulfides, which are involved in the synthesis of ligands and pharmaceutical chiral synthetic precursors [1][2] and in (b) the transfer-hydrogenation reaction catalyzed by bifunctional chiral ruthenium complexes, employed in the synthesis of peptide mimics with an interesting

Effective immobilisation of a metathesis catalyst bearing an ammonium-tagged NHC ligand on various solid supports

• Krzysztof Skowerski,
• Jacek Białecki,
• Stefan J. Czarnocki,
• Karolina Żukowska and
• Karol Grela

Beilstein J. Org. Chem. 2016, 12, 5–15, doi:10.3762/bjoc.12.2

• resulted system. In parallel work, the recyclability of an immobilised Ru-catalyst bearing quaternary ammonium-tagged NHC ligand was described. Selected classical and heterogeneous ruthenium complexes. Applications of NHC ammonium-tagged catalysts. Influence of temperature and concentration on RCM of 9

New metathesis catalyst bearing chromanyl moieties at the N-heterocyclic carbene ligand

• Agnieszka Hryniewicka,
• Szymon Suchodolski,
• Agnieszka Wojtkielewicz,
• Jacek W. Morzycki and
• Stanisław Witkowski

Beilstein J. Org. Chem. 2015, 11, 2795–2804, doi:10.3762/bjoc.11.300

• the above-mentioned moieties. The ruthenium complexes 4–6 (Figure 2) that we reported earlier appeared to be the so-called dormant catalysts. Their activity in RCM reactions was low at room temperature and higher at elevated temperature [21]. In catalyst 7 the chelating oxygen atom was provided by the

Recent advances in metathesis-derived polymers containing transition metals in the side chain

• Ileana Dragutan,
• Valerian Dragutan,
• Bogdan C. Simionescu,
• Albert Demonceau and
• Helmut Fischer

Beilstein J. Org. Chem. 2015, 11, 2747–2762, doi:10.3762/bjoc.11.296

• -, osmium- and rhodium-containing polymers ROMP syntheses of homopolymers and block copolymers bearing bipyridine–ruthenium complexes starting from norbornene or oxanorbornene functionalized with Ru complexes have been reported by several authors [55][56]. In these investigations it was revealed that the Ru

Beyond catalyst deactivation: cross-metathesis involving olefins containing N-heteroaromatics

• Kevin Lafaye,
• Cyril Bosset,
• Lionel Nicolas,
• Amandine Guérinot and
• Janine Cossy

Beilstein J. Org. Chem. 2015, 11, 2223–2241, doi:10.3762/bjoc.11.241

• methylidene intermediates 3 and 4 to give CH3PCy3+Cl− and inactive ruthenium complexes. Similar observations were made in the absence or in the presence of ethylene in the reaction medium (Scheme 1). Similar studies concerning the Grubbs–Hoveyda II catalyst were difficult due to the instability of the

• on the hindered benzylidene. With more sterically hindered amines b–d, the ruthenium complexes 11b–d, resulting from phosphine displacement, proved to be stable even after 24 h at 60 °C (Scheme 4). The half-life of methylidene 2 derived from GII in the presence of the amines were then evaluated using

• , ruthenium complexes 19b–d possessing one amine were formed and proved to be thermally stable. When the G-HII catalyst was treated with pyridine (e), the stable bis-pyridyl adduct 20e was formed in equilibrium with G-HII and no significant decomposition of the catalyst was observed (Scheme 8). In contrast