Search results for "olefin"

A short synthesis of pyridines from deprotonated α-aminonitriles by an alkylation/RCM sequence

2016

Abstract α-Aminonitriles can serve as versatile key precursors for the synthesis of nitrogen containing heterocycles. After unsuccessful trials involving the [1,2]-Stevens rearrangement of nitrile-stabilized ammonium ylides, we herein report a simple three-step synthesis of substituted pyridines based on an alkylation/ring-closing metathesis/aromatization sequence.

Influence of the matrix on photo-oxidative degradation of polyolefin based nanocomposite films

2008

Diversity-Oriented Synthesis of Highly Functionalized Alicycles across Dipolar Cycloaddition/Metathesis Reaction

2021

AbstractThis Account gives an insight into the selective functionalization of some readily available commercial cyclodienes across simple chemical transformations into functionalized small-molecular scaffolds. The syntheses involved selective cycloadditions, followed by ring-opening metathesis (ROM) of the resulting azetidin-2-one derivatives or isoxazoline frameworks and selective cross metathesis (CM) by discrimination of the C=C bonds on the alkenylated heterocycles. The CM protocols have been described when investigated under various conditions with the purpose on exploring chemodifferentiation of the olefin bonds and a study on the access of the corresponding functionalized β-lactam or…

Templated synthesis of a large and flexible covalent porphyrinic cage bearing orthogonal recognition sites.

2012

A large covalent cage incorporating two porphyrins attached by four long and flexible polyether chains each bearing two 3-pyridyl ligands was synthesized from a DABCO-templated olefin metathesis reaction. The X-ray structure of the cage with the DABCO coordinated inside the cavity to the two zinc(II) porphyrins reveals a highly symmetric structure.

Vanadium catalysts for ethylene-norbornene copolymerization

2020

Cyclic olefin copolymers (COCs) are a promising group of materials with specific, projectable properties. In this group, copolymers of ethylene and norbornene are of particular interest. A variety of transition metal complexes are used for their synthesis, mostly elements from group 4. This review presents the application of vanadium catalysts with various types of ligands in the synthesis of ethylene-norbornene copolymers. The influence of ligands and reaction conditions on the activity of catalyst and selected properties of copolymers are described in this paper.

Correction to Impact of organoaluminum compounds on phenoxyimine ligands in coordinative olefin polymerization. A theoretical study

2013

Organolanthanides, catalysts for specific olefin-diene copolymerization: access to new materials

2001

Abstract Non-hindered ansa dicyclopentadienylallyl complexes of samarium, [(CMe2C5H4)2Sm(allyl)]n, and (CMe2C5H4)2Sm(allyl)L (L=THF or allylLi) polymerize isoprene without an aluminum cocatalyst. The polymerizations are highly stereospecific, affording nearly quantitatively 1–4 trans polyisoprene. In the presence of linear 1-olefins, copolymers are formed, with 6–10% of olefin inserted; the 1–4 trans structure of the polyisoprene chain is not altered, and only one olefin molecule is inserted between two polyisoprene fragments. In the common initiator of these three catalytic systems, the (CMe2C5H4)2Sm(allyl) moiety, only one vacant site would be available. As a consequence of the presence o…

Theoretical study of isomerism in phenoxyimine-based precursors of coordinative olefin polymerization catalysts

2010

Precursors of post-metallocene olefin polymerization catalysts, unlike their predecessors, are usually octahedral transition metal complexes with multidentate ligands. Such ligands may wrap around the central atom in many ways, thus yielding several isomeric species. For a wide range of phenoxyimine (FI) ligands with different substituents, all the theoretically predicted diastereomers of group 4 and 5 complexes are available synthetically. However, only one of the isomers is usually preferred, and this is determined by the nature of the substituents in the FI ligand. The origin and mechanism of such preference has not been completely elucidated. We attempted to describe it quantitatively o…

Dichlorovanadium(IV) diamine-bis(phenolate) complexes for ethylene (co)polymerization and 1-olefin isospecific polymerization

2018

Abstract Two vanadium complexes bearing amine-bis(phenolate) ligands with the amino side-arm donor, [V{Me2NCH2CH2N(CH2-2-O-3,5-tBu2-C6H2)2}Cl2] (1) and [V{Me2NCH2CH2N(CH2-2-O-3,5-tBu2-C6H2)(CH2-2-O-C6H4)}Cl2] (2), were synthesised and characterized by FTIR and 1H NMR spectroscopy. Upon activation with Al(iBu)3/Ph3CB(C6F5)4, these complexes became active catalysts for 1-octene polymerization giving highly stereoregular polymers (mmmm ∼ 90%) having regioirregularly arranged units. The catalytic activity of the catalysts in ethylene homo- and copolymerization, and their ability to incorporate a comonomer were highly dependent on both the activator type and the complex structure. 1/EtAlCl2 exhi…

Synthesis of Enantiopure ω-(4-Fluorophenyl)-6,11-Methylene Lipoxin B4 Methyl Ester

2021

AbstractThe synthesis of Lipoxin B4 analogues (LXB4) to gain access to stabilized inflammation-resolving compounds is an active field of research. Focusing on variation and stabilization of the conjugated E,Z,E,E C6–C13 tetraene moiety of natural LXB4, a methylene bridge introduced between C6 and C11 suppresses any Z/E isomerization of the C8–C9 olefin. Furthermore, rapid ω-oxidation (C20) should be avoided by replacing the C18–C20 segment by an aromatic moiety. Optically active C1–C12 building blocks were accessed from methyl cycloheptatriene-1-carboxylate (C6–C11, C21) and glutaryl chloride (C1–C5) as described earlier. The ω-segment was generated via a five-step sequence starting from 4-…