Search results for "metathesis"
showing 10 items of 150 documents
ChemInform Abstract: A New Tandem Cross Metathesis-Intramolecular Aza-Michael Reaction for the Synthesis of α,α-Difluorinated Lactams.
2012
Difluorinated amides are treated with methyl vinyl ketone or analogous esters to produce the desired γ- and δ-lactam units including optically active versions.
Applications and stereoselective syntheses of P-chirogenic phosphorus compounds.
2016
International audience; Phosphorus compounds bearing chirality on the P-center are usually qualified as P-chirogenic or P-stereogenic. This chemical class concerns natural products, agrochemistry, molecular materials, biology and pharmacy, although it is certainly in coordination chemistry and in asymmetric catalysis using chiral transition metal complexes that P-chirogenic phosphorus compounds are the most used. The chiral phosphine ligands and their uses in asymmetric metal-catalyzed reactions have been widely reviewed in literature. However, an overview covering the applications as well as the stereoselective syntheses of all classes of phosphorus compounds has not yet been provided. Thi…
Ring-opening metathesis of some strained bicyclic systems; stereocontrolled access to diolefinated saturated heterocycles with multiple stereogenic c…
2018
Ring-opening metathesis (ROM) of various unsaturated, constrained bicyclic ring systems has been investigated with the use of commercial ruthenium-based catalysts. Starting from various cyclodienes, the corresponding derived bicyclic lactone, lactam, and isoxazoline derivatives were submitted to ROM under ethenolysis. These functionalized, strained bicyclic systems afforded novel highly-functionalized diolefinated heterocyclic scaffolds in ROM reactions with stereocontrol, through the conservation of the configuration of the stereogenic centers of the starting compounds.
Poly[1-ethyl-3-methylimidazolium [tri-μ-isothiocyanato-manganate(II)]]
2019
The title compound, {(C9H11N2)[Mn(NCS)3]} n , has been obtained as a side product of the salt metathesis reaction of 1-ethyl-3-methylimidazolium bromide, (EMIm)Br, and K2[Mn(NCS)4]. The structure consists of discrete 1-ethyl-3-methylimidazolium cations and an anionic two-dimensional network of manganese(II)-based complex anions, interconnected by thiocyanate ions. Every Mn2+ ion is coordinated by three S atoms of three NCS− ions and three N atoms of further three NCS− ions in a meridional octahedral fashion.
One-pot cross-enyne metathesis (CEYM)-Diels-Alder reaction of gem-difluoropropargylic alkynes.
2013
Propargylic difluorides 1 were used as starting substrates in a combination of cross-enyne metathesis and Diels–Alder reactions. Thus, the reaction of 1 with ethylene in the presence of 2nd generation Hoveyda–Grubbs catalyst generates a diene moiety which in situ reacts with a wide variety of dienophiles giving rise to a small family of new fluorinated carbo- and heterocyclic derivatives in moderate to good yields. This is a complementary protocol to the one previously described by our research group, which involved the use of 1,7-octadiene as an internal source of ethylene.
Reactions of m-Terphenyl-Stabilized Germylene and Stannylene with Water and Methanol: Oxidative Addition versus Arene Elimination and Different React…
2015
Reactions of the divalent germylene Ge(ArMe6)2 (ArMe6 = C6H3-2,6-{C6H2-2,4,6-(CH3)3}2) with water or methanol gave the Ge(IV) insertion product (ArMe6)2Ge(H)OH (1) or (ArMe6)2Ge(H)OMe (2), respectively. In contrast, its stannylene congener Sn(ArMe6)2 reacted with water or methanol to produce the Sn(II) species {ArMe6Sn(μ-OH)}2 (3) or {ArMe6Sn(μ-OMe)}2 (4), respectively, with elimination of ArMe6H. Compounds 1–4 were characterized by IR and NMR spectroscopy as well as by X-ray crystallography. Density functional theory calculations yielded mechanistic insight into the formation of (ArMe6)2Ge(H)OH and {ArMe6Sn(μ-OH)}2. The insertion of an m-terphenyl-stabilized germylene into the O–H bond was…
Facile and efficient chemical functionalization of aliphatic polyesters by cross metathesis
2016
International audience; An effective preparation of new tailor-made macromolecular materials via a combination of two (atom-efficient) catalytic transformations is reported. First, new aliphatic polyesters with alternated composition have been prepared using a salen aluminum catalyst system. Next, the pendant vinyl moieties in those copolymers have been selectively transformed into various functional groups by metathesis in the presence of homogeneous Grubbs catalysts. The latter metathesis reaction has been optimized in terms of catalytic activity and selectivity, to define the conditions for an effective and safe procedure that does not affect the macromolecular architecture. All polymer …
Silseskwioksany i ich zastosowanie w syntezie materiałów polimerowych
2015
Artykuł stanowi przegląd literatury dotyczącej syntezy oraz charakterystyki materiałów polimerowych zawierających silseskwioksany (POSS). Przedstawiono metody otrzymywania hybrydowych materiałów polimerowych z udziałem funkcjonalizowanych POSS na drodze click chemistry, polikondensacji, poliaddycji, metatezy z otwarciem pierścienia ipolimeryzacji rodnikowej zarówno konwencjonalnej, jak i kontrolowanej (ATRP).
Relay Catalysis: Enantioselective Synthesis of Cyclic Benzo-Fused Homoallylic Alcohols by Chiral BrOnsted Acid-Catalyzed Allylboration/Ring Closing M…
2013
Six- and seven-membered benzo-fused cyclic homoallylic alcohols can be readily synthesized by a tandem chiral BrOnsted acid-catalyzed allyl (crotyl)boration/ring closing metathesis sequence performed under orthogonal relay catalysis conditions. Excellent enantio- and diastereoselectivities are obtained in most of the cases. In addition, the parent crotylboration/RCM process is also described. The required substrates, ortho-vinylbenzaldehydes, are readily available in one step from commercially available starting materials. Both catalysts and reactants are also available from commercial suppliers. The reaction shows broad functional group compatibility and is also suitable for heteroaromatic…
New methodologies in transition metal catalysis. Organofluorine chemistry as the benchmark application.
2017
A lo largo de las últimas décadas, los compuestos organofluorados han encontrado numerosas aplicaciones dentro del campo de las industrias farmacéutica y agroquímica, así como en ciencias de los materiales. Dadas las singulares propiedades del átomo de flúor, éste es capaz de inducir alteraciones significativas en propiedades físico-químicas de las moléculas como lipofilia, distribución de cargas, acidez-basicidad, capacidad de formar enlaces de hidrógeno e incluso, equilibrios conformacionales. Sin embargo, la presencia de flúor en productos naturales es escasa. De hecho, la gran mayoría de las moléculas orgánicas que contienen flúor son sintéticas. De ahí el gran interés por parte de la c…