22768-02-1Relevant articles and documents
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Grynkiewicz et al.
, p. 1411 (1975)
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N-Heterocyclic Carbene-Phosphinidene Complexes of the Coinage Metals
Doddi, Adinarayana,Bockfeld, Dirk,Nasr, Alexandre,Bannenberg, Thomas,Jones, Peter G.,Tamm, Matthias
, p. 16178 - 16189 (2015)
Coinage metal complexes of the N-heterocyclic carbene-phosphinidene adduct IPr·PPh (IPr=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) were prepared by its reaction with CuCl, AgCl, and [(Me2S)AuCl], which afforded the monometallic complexes [(IPr·PPh)MCl] (M=Cu, Ag, Au). The reaction with two equivalents of the metal halides gave bimetallic [(IPr·PPh)(MCl)2] (M=Cu, Au); the corresponding disilver complex could not be isolated. [(IPr·PPh)(CuOTf)2] was prepared by reaction with copper(I) trifluoromethanesulfonate. Treatment of [(IPr·PPh)(MCl)2] (M=Cu, Au) with Na(BArF) or AgSbF6 afforded the tetranuclear complexes [(IPr·PPh)2M4Cl2]X2 (X=BArF or SbF6), which contain unusual eight-membered M4Cl2P2 rings with short cuprophilic or aurophilic contacts along the chlorine-bridged M...M axes. Complete chloride abstraction from [(IPr·PPh)(AuCl)2] was achieved with two equivalents of AgSbF6 in the presence of tetrahydrothiophene (THT) to form [(IPr·PPh){Au(THT)}2][SbF6]2. The cationic tetra- and dinuclear complexes were used as catalysts for enyne cyclization and carbene transfer reactions.
Electrochemical anion pool synthesis of amides with concurrent benzyl ester synthesis
Mevan Dissanayake,Melville, Alex D.,Vannucci, Aaron K.
supporting information, p. 3165 - 3171 (2019/06/18)
An electrosynthesis method for amide bond formation has been developed in an attempt to increase the atom economy for this class of reactions. This "anion pool" method electrochemically generates strong nucleophiles from amine substrates. The amine nucleophiles then react with acid anhydrides to generate amides, and the by-product from this reaction undergoes further chemical transformations to generate pharmaceutically relevant benzoic esters. These one-pot reactions are operationally simple, are performed at room temperature, and avoid rare transition metals and added bases. The amide synthesis is amenable to primary and secondary amines and a variety of anhydrides with yields up to 90% obtained. Atom economy and process mass index (PMI) values calculated for this procedure indicate that this process can be considered greener compared to traditional amide synthesis routes used by industry. Furthermore, this electrochemical approach showed unique selectivity when substrates that contained two inequivalent amine moieties were examined.
Carbon Dioxide Utilisation for the Synthesis of Unsymmetrical Dialkyl and Cyclic Carbonates Promoted by Basic Ionic Liquids
Goodrich, Peter,Gunaratne, H. Q. Nimal,Jin, Lili,Lei, Yuntao,Seddon, Kenneth R.
, p. 181 - 185 (2018/03/09)
An efficient and greener synthesis of unsymmetrical organic carbonates mediated by Hünig's base-appended basic ionic liquids, via carbon dioxide conversion, is described here. These ionic liquids were found to be effective bases for the fixation of carbon dioxide by various alcohols and benzyl bromide, at room temperature. When the alcohol and the halide functionalities are present within the same substrate, the reaction cleanly produces a cyclic carbonate. These functionalised basic ionic liquids were fully recyclable with no loss product yields.
