2243-27-8Relevant articles and documents
EFFET DE L'EAU ET D'AUTRES ADDITIFS SUR L'ALKYLATION DE KCN EN TRANSFERT DE PHASE SOLIDE-LIQUIDE SANS SOLVANT.
Bram, G.,Loupy, A.,Pedoussaut, M.
, p. 4171 - 4174 (1986)
The alkylation of KCN by solid-liquid phase transfer catalysis without added solvent is optimal when a definite amount of water is added.The efficiencies of ten other additives are compared with those of water.
Application of chelating diphosphine ligands in the nickel-catalysed hydrocyanation of alk-1-enes and ω-unsaturated fatty acid esters
Goertz, Wolfgang,Kamer, Paul C. J.,Van Leeuwen, Piet W. N. M.,Vogt, Dieter
, p. 1521 - 1522 (1997)
The hydrocyanation of alk-1-enes and ω-unsaturated fatty acid esters using zerovalent nickel complexes yields the corresponding nitriles and cyanoesters, which can be useful starting materials in organic synthesis.
Mechanisms of Polymer-Supported Catalysis. 1. Reaction of 1-Bromooctane with Aqueous Sodium Cyanide Catalyzed by Polystyrene-Bound Benzyltri-n-butylphosphonium Ion
Tomoi, M.,Ford, Warren T.
, p. 3821 - 3828 (1981)
The rate of reaction of 1-bromooctane with aqueous sodium cyanide catalyzed by insoluble polystyrene-bound benzyltri-n-butylphosphonium salts has been studied as a function of the method of mixing of the triphase system, catalyst particle size, degree of polymer cross-linking, solvent, and temperature.Reaction rates increase as the speed of mechanical stirring increases to a maximum rate at 600 rpm.Turbulent vibromixing and ultrasonic mixing do not cause any additional reaction rate increase.Reaction rates increase as catalyst particle sizes decrease, even at the maximum stirring speed.Reaction rates decrease as percent of divinylbenzene cross-linking in the polymer increases from 2percent to 10percent.Reaction rates increase with increasing swelling power of the solvent in the order decane /= 28 times faster than polymer-bound benzyltrimethylammonium when mass transfer and intraparticle diffusion do not limit the rates.
Binding Profiles for Oligoethylene Glycols and Oligoethylene Glycol Monomethyl Ethers and an Assessment of Their Abilities To Catalyze Phase-Transfer Reactions
Gokel, George W.,Goli, Deepa M.,Schultz, Rose Ann
, p. 2837 - 2842 (1983)
The equilibrium binding or stability constants (K8) between Na+ and oligoethylene glycols , monomethyl ethers , and dimethyl ethers have been determined in anhydrous methanol solution.The ranges of compounds involved are as follows: diols, n = 3-312; monoethers, n = 6-15; diethers, n = 3-21.Although the slopes vary some from species to species, the plot of log K8 vs. log molecular weight is an essentially straight line.There is no peak in binding observed when a particular number of oxygens might be present to provide, for example, an octahedron of donor groups or a quasi-crown coil.The molecular weight is not crucial to the binding since equal weights of different glycols afford the same net sodium binding.This similarity does not extend to reactivity in the liquid-liquid phase-transfer catalytic system in which it appears that one molecule of polyethylene glycol derivative effects one reaction at a time.Thus equal weights of shorter chains are much more effective than longer chain lengths of similar species.
TRIPHASE CATALYSIS OF POLYMER-BOUND AMINE OXIDE IN CYANIDE DISPLACEMENT ON 1-BROMOOCTANE
Maeda, Hirokazu,Hayashi, Yoshiyuki,Teramura, Kazuhiro
, p. 677 - 678 (1980)
Cross-linked polystyrene supported tertiary amines and amine oxides are found to be a very efficient catalyst for a nucleophilic substitution reaction.The amine oxide resin (MPE-5-AO) was one of the most effective and economical catalysts and can be used several times without the loss of the catalytic activity.
A Molecular Iron-Based System for Divergent Bond Activation: Controlling the Reactivity of Aldehydes
Chatterjee, Basujit,Jena, Soumyashree,Chugh, Vishal,Weyhermüller, Thomas,Werlé, Christophe
, p. 7176 - 7185 (2021/06/30)
The direct synthesis of amides and nitriles from readily available aldehyde precursors provides access to functional groups of major synthetic utility. To date, most reliable catalytic methods have typically been optimized to supply one product exclusively. Herein, we describe an approach centered on an operationally simple iron-based system that, depending on the reaction conditions, selectively addresses either the C=O or C-H bond of aldehydes. This way, two divergent reaction pathways can be opened to furnish both products in high yields and selectivities under mild reaction conditions. The catalyst system takes advantage of iron's dual reactivity capable of acting as (1) a Lewis acid and (2) a nitrene transfer platform to govern the aldehyde building block. The present transformation offers a rare control over the selectivity on the basis of the iron system's ionic nature. This approach expands the repertoire of protocols for amide and nitrile synthesis and shows that fine adjustments of the catalyst system's molecular environment can supply control over bond activation processes, thus providing easy access to various products from primary building blocks.
Ni-Catalyzed Isomerization-Hydrocyanation Tandem Reactions: Access to Linear Nitriles from Aliphatic Internal Olefins
Gao, Jihui,Ni, Jie,Yu, Rongrong,Cheng, Gui-Juan,Fang, Xianjie
supporting information, p. 486 - 490 (2021/02/05)
A highly regioselective nickel-based catalyst system for the isomerization/hydrocyanation of aliphatic internal olefins is described. This benign tandem reaction provides facile access to a wide variety of aliphatic nitriles in good yields with excellent regioselectivities. Thanks to Lewis acid-free conditions, the protocol features board functional groups tolerance, including secondary amine and unprotected alcohol groups.
Design, synthesis and antiparasitic evaluation of click phospholipids
Afroudakis, Pantelis,Barrias, Emile,Bifeld, Eugenia,Borsari, Chiara,Calogeropoulou, Theodora,Clos, Joachim,Costi, Maria Paola,Ellinger, Bernhard,Fotopoulou, Theano,Fragiadaki, Irini,Georgikopoulou, Kalliopi,Gul, Sheraz,Hachenberg, Julia,Kuzikov, Maria,Magoulas, George E.,Prousis, Kyriakos C.,Roussaki, Marina,Santarem, Nuno,Scoulica, Effie,Tejera Nevado, Paloma,da Silva, Anabela Cordeiro,de Souza, Wanderley
, (2021/07/26)
A library of seventeen novel ether phospholipid analogues, containing 5-membered heterocyclic rings (1,2,3-triazolyl, isoxazolyl, 1,3,4-oxadiazolyl and 1,2,4-oxadiazolyl) in the lipid portion were designed and synthesized aiming to identify optimised miltefosine analogues. The compounds were evaluated for their in vitro antiparasitic activity against Leishmania infantum and Leishmania donovani intracellular amastigotes, against Trypanosoma brucei brucei and against different developmental stages of Trypanosoma cruzi. The nature of the substituents of the heterocyclic ring (tail) and the oligomethylene spacer between the head group and the heterocyclic ring was found to affect the activity and toxicity of these compounds leading to a significantly improved understanding of their structure–activity relationships. The early ADMET profile of the new derivatives did not reveal major liabilities for the potent compounds. The 1,2,3-triazole derivative 27 substituted by a decyl tail, an undecyl spacer and a choline head group exhibited broad spectrum antiparasitic activity. It possessed low micromolar activity against the intracellular amastigotes of two L. infantum strains and T. cruzi Y strain epimastigotes, intracellular amastigotes and trypomastigotes, while its cytotoxicity concentration (CC50) against THP-1 macrophages ranged between 50 and 100 μM. Altogether, our work paves the way for the development of improved ether phospholipid derivatives to control neglected tropical diseases.
A Titanium-Catalyzed Reductive α-Desulfonylation
Kern, Christoph,Selau, Jan,Streuff, Jan
supporting information, p. 6178 - 6182 (2021/03/16)
A titanium(III)-catalyzed desulfonylation gives access to functionalized alkyl nitrile building blocks from α-sulfonyl nitriles, circumventing traditional base-mediated α-alkylation conditions and strong single electron donors. The reaction tolerates numerous functional groups including free alcohols, esters, amides, and it can be applied also to the α-desulfonylation of ketones. In addition, a one-pot desulfonylative alkylation is demonstrated. Preliminary mechanistic studies indicate a catalyst-dependent mechanism involving a homolytic C?S cleavage.
Nickel/Cobalt-Catalyzed Reductive Hydrocyanation of Alkynes with Formamide as the Cyano Source, Dehydrant, Reductant, and Solvent
Zhang, Jin,Luo, Cui-Ping,Yang, Luo
supporting information, p. 283 - 288 (2020/12/01)
A Ni/Co co-catalyzed reductive hydrocyanation of various alkynes was developed for the production of saturated nitriles. Hydrocyanic acid is generated in situ from safe and readily available formamide. Formamide played multiple roles as a cyano source, dehydrant, and reductant for the NiII pre-catalyst and vinyl nitriles, along with acting as the co-solvent in this reaction. Detailed mechanistic investigation supported a pathway via hydrocyanation of C≡C bond and the subsequent reduction of C=C bond. Wide substrate scope, the employment of a cheap and stable nickel salt as pre-catalyst, a safe cyano source and convenient experimental operation render this hydrocyanation practical for the laboratory synthesis of saturated nitriles. (Figure presented.).
