158943-16-9

Upstream product

• 1476-11-5 Z-1,4-dichlorobutene 
• 140-29-4 phenylacetonitrile 
• 71-43-2 benzene 
• 28049-67-4 2-Phenyl-2-(2-propenyl)-4-pentenenitrile 
• 764-41-0 1,4-dichloro-2-butene 

Downstream Products

• 158943-17-0 1-phenylcyclopent-3-ene-1-carboxylic acid 
• 858422-85-2 1-phenyl-cyclopent-3-enecarbonyl chloride 
• 1423777-34-7 1-phenylcyclopent-3-en-1-carbaldehyde 

Relevant academic research and scientific papers

2-Methyltetrahydrofuran: Sustainable solvent for ruthenium-catalyzed olefin metathesis

Applicability of 2-methyltetrahydrofuran for olefin metathesis was examined with a set of ruthenium Hoveyda-type second generation catalysts. Influence of temperature was studied and the results were compared with those obtained in classical solvents for metathesis: dichloromethane and toluene.

Ruthenium-catalysed olefin metathesis in environmentally friendly solvents: 2-methyltetrahydrofuran revisited

Application profiles of a set of popular second-gen-eration ruthenium catalysts were experimentally investigated in an environmentally friendly solvent, 2-methyltetrahydrofuran (2-MeTHF), and compared with the activity of the same catalysts in toluene, a popular solvent used in industrial olefin metathesis. It was found that a catalyst containing a 2-isopropoxy-5-nitrobenzylidene moiety and a symmetrical N-heterocyclic (NHC) ligand with 2,6-diisopropylphenyl substituents (SIPr) ex-hibits the highest catalytic activity in 2-MeTHF also at a lower temperature (30 °C). Ab initio studies showed that initiation rates of Ru catalysts bearing NHC ligands in 2-MeTHF can be correlated with partial charges and bond lengths between selected crucial atoms in the studied ruthenium complexes. The results demonstrate that aromatic or chlorinated solvents, typically used in metathesis reactions, can be successfully replaced in many cases by 2-MeTHF.

Ruthenium Complexes Bearing Thiophene-Based Unsymmetrical N-Heterocyclic Carbene Ligands as Selective Catalysts for Olefin Metathesis in Toluene and Environmentally Friendly 2-Methyltetrahydrofuran

Three mono-N-heterocyclic carbene (NHC) ruthenium 2-isopropoxybenzylidene (10 a–c) and one bis(NHC) indenylidene complex (8) bearing an unsymmetrical N-heterocyclic carbene ligand were synthesized and structurally characterized by single-crystal X-ray diffraction. The catalytic activity of the newly obtained complexes were evaluated in ring-closing metathesis (RCM) and ene–yne (RCEYM) reactions in toluene and environmentally friendly 2-MeTHF under air. The results confirmed that although all tested reactions can be successfully mediated by catalysts 10 a–c, their general reactivity is lower than the benchmark all-purpose Ru catalysts with symmetrical NHC ligands. However, the latter cannot compete with specialized ruthenium complex 10 a in industrially relevant self-CM of terminal olefins in neat conditions.

Efficient and Clean Nickel Catalyzed α-Allylation Reaction of Nitriles

A clean method has been developed for the α-allylation of phenyl and alpha alkyl phenyl acetonitrile with allylic alcohols. The reaction is catalyzed by nickel complexes in situ generated from a combination of Ni(cod)2 and the dppf ligand and performed at 80 °C in methanol as reaction solvent.Accordingly to this simple and base-free protocol that only yields water as a side-product, many allylic nitriles were synthetized with good yields. (Figure presented.).

Semiheterogeneous Purification Protocol for the Removal of Ruthenium Impurities from Olefin Metathesis Reaction Products Using an Isocyanide Scavenger

A low-waste, time-economical, and scalable semiheterogeneous purification protocol for the removal of ruthenium residues from olefin metathesis (OM) reactions has been developed. It is based on the non-covalent immobilization of the commercially available

Highly efficient and time economical purification of olefin metathesis products from metal residues using an isocyanide scavenger

A sustainable protocol of olefin metathesis in non-degassed, undistilled ethyl acetate under air with commercially available self-scavenging ruthenium catalysts is described. Furthermore, a time economical, cost-effective and scalable method of removal of ruthenium residues is presented. Treatment of post-reaction mixtures with an isocyanide scavenger and then with acid followed by a simple filtration is shown to yield OM products with ruthenium contamination below 5 ppm even in highly challenging cases. Finally, a telescope RCM/Suzuki-Miyaura sequence with a rapid and efficient purification protocol for simultaneous removal of Ru and Pd residues from solution is described.

Ruthenium Olefin Metathesis Catalysts Systematically Modified in Chelating Benzylidene Ether Fragment: Experiment and Computations

Five Hoveyda–Grubbs-type complexes bearing cyclopropyl to cycloheptyl ether moieties in the chelating benzylidene ligand have been synthesized and investigated by spectroscopic and crystallographic methods. Their experimentally measured catalytic activity

Hoveyda-grubbs-type precatalysts with unsymmetrical N-Heterocyclic carbenes as effective catalysts in olefin metathesis

In our search for more-selective olefin metathesis catalysts, a series of Hoveyda-Grubbs-type second-generation complexes bearing unsymmetrical N-heterocyclic carbene (NHC) ligands were synthesized and tested in model reactions. It was found that the N-benzyl substituent in NHC has a positive influence on the selectivity of the newly obtained catalysts in the self-metathesis reaction of α-olefins. As expected, a typical relationship between activity and selectivity with respect to the N-aryl substituent used was observed. Dipp-containing complexes exhibited higher stability at elevated temperature, while Mes-bearing complexes typically gave better yields than their Dipp analogues.

High-Performance Isocyanide Scavengers for Use in Low-Waste Purification of Olefin Metathesis Products

Three isocyanides containing a tertiary nitrogen atom were investigated for use as small-molecule ruthenium scavenging agents in the workup of olefin metathesis reactions. The proposed compounds are odorless, easy to obtain, and highly effective in removi

Synthesis, structure, and catalytic activity of new ruthenium(II) indenylidene complexes bearing unsymmetrical N - heterocyclic carbenes

New robust and air-stable ruthenium(II) indenylidene type second-generation precatalysts with unsymmetrical N-heterocyclic carbene (NHC) ligands were synthesized. The reaction profiles of these complexes were studied in commercial-grade solvents in air with model substrates leading to the di-, tri-, and tetrasubstituted olefins. In addition, application of selected precatalysts for olefin metathesis reactions on a broad spectrum of substrates with different functional groups was examined. Studies of solvent effects for the selected precatalysts as well as thermal activation of the corresponding complexes showed significant differences in their activities. Observed relationships in connection with single-crystal X-ray analysis revealed the influence of the unsymmetrical NHC ligands on the initiation rate of precatalysts. Dissociation of the phosphine ligand, the rate-determining step for our most active precatalysts, is accelerated by the steric repulsion of the dangling benzyl arm and the tricyclohexylphosphine ligand. A precatalyst with a hemilabile benzyl arm evinced decreased activity, probably due to coordination of the heteroatom to the ruthenium core taking place after dissociation of the phosphine ligand.