10283-95-1Relevant articles and documents
Electrochemical anion pool synthesis of amides with concurrent benzyl ester synthesis
Mevan Dissanayake,Melville, Alex D.,Vannucci, Aaron K.
, p. 3165 - 3171 (2019)
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.
Electrochemical Fluorocyclization of N-Allylcarboxamides to 2-Oxazolines by Hypervalent Iodine Mediator
Haupt, John D.,Berger, Michael,Waldvogel, Siegfried R.
, p. 242 - 245 (2019)
A resource saving protocol for the synthesis of 5-fluoromethyl-2-oxazolines by using electrochemistry has been realized. Thereby, a hypervalent iodine species I(III) is generated by anodic oxidation in the presence of Et3N·5HF and mediates the
Direct oxidative amidation of benzyl alcohols using EDTA@Cu(II) functionalized superparamagnetic nanoparticles
Azizi, Kobra,Karimi, Meghdad,Nikbakht, Fatemeh,Heydari, Akbar
, p. 336 - 343 (2014)
Superparamagnetic Fe3O4@EDTA-Cu(II) nanoparticles were readily prepared and identified as an effective catalyst for the tandem transformation of benzyl alcohols and amine hydrochloride salts into the corresponding amides with tert-bu
Chloroform as a Carbon Monoxide Precursor: In or Ex Situ Generation of CO for Pd-Catalyzed Aminocarbonylations
Gockel, Samuel N.,Hull, Kami L.
, p. 3236 - 3239 (2015)
Conditions for the rapid hydrolysis of chloroform to carbon monoxide (CO) using heterogeneous CsOH·H2O are described. CO and 13CO can be generated cleanly and rapidly under mild conditions and can be captured either in or ex situ in palladium-catalyzed aminocarbonylation reactions. Utilizing only 1-3 equiv of CO allows for the aminocarbonylation of aryl, vinyl, and benzyl halides with a wide variety of primary and secondary amines giving amide products in good to excellent yields. (Chemical Equation Presented).
Nickel/briphos-catalyzed transamidation of unactivated tertiary amides
Kim, Hyunwoo,Lee, Sunwoo,Shin, Taeil,Yang, Dahyeon
, p. 6053 - 6057 (2020)
The transamidation of tertiary amides was achieved via nickel catalysis in combination with briphos ligands. N-Methyl-N-phenylbenzamide derivatives reacted with primary amines in the presence of NiCl2/briphos L4 to provide the transamidated products in moderate to good yields. Primary aromatic amines delivered higher product yields than aliphatic amines.
The dual role of thiourea in the thiotrifluoromethylation of alkenes
Ricci, Paolo,Khotavivattana, Tanatorn,Pfeifer, Lukas,Médebielle, Maurice,Morphy, John Richard,Gouverneur, Véronique
, p. 1195 - 1199 (2017)
Alkenes substituted with a thiourea undergo C-CF3 followed by intramolecular C-S bond formation with the Togni reagent and trifluoroacetic acid (TFA) at room temperature; thiols and thioamides are not suitable S-sources for this reaction. This anti-addition process involves a CF3 radical, and affords CF3-substituted thiazolines and thiazines for medicinal applications. A metal or photoredox catalyst is not required as the thiourea acts as a reductant, as well as serving as an S-source capable of adding to a C-centered radical. Mechanistic work comparing the reactivity of thiourea, urea, thioamide and thiol in the context of alkene trifluoromethylation demonstrates that in this series, the thiourea is unique for its ability to release CF3 radical from the Togni reagent, and to orchestrate trifluoromethylation followed by S-cyclization with both activated and unactivated alkenes.
Photochemistry of Epoxynaphthoquinones. 8. Endo-Stereoselective Photocycloaddition of 2,3-Epoxy-2,3-dihydro-2,3-dimethyl-1,4-naphthoquinone to Olefins Containing Amide Group
Maruyama, Kazuhiro,Osuka, Atsuhiro,Nakagawa, Katsuhiko
, p. 1021 - 1026 (1987)
Irradiation of a benzene solution of 2,3-epoxy-2,3-dihydro-2,3-dimethyl-1,4-naphthoquinone with olefins containing amide group, i.e., N-substituted acrylamides and N-allylcarboxamides predominantly gave the endo-cycloadducts.Upon further irradiation, the cycloadducts underwent photorearrangement to give spirophthalides and alkylidenephthalides.
Sequential catalytic carbonylation reactions for sustainable synthesis of biologically relevant entities
Carrilho, Rui M. B.,Damas, Liliana,Gonzalez, Andreia C. S.,Pereira, Mariette M.,Pineiro, Marta,Rodrigues, Fábio M. S.
, (2020)
The sustainable synthesis of highly functionalised formylcarboxamide compounds with biological relevance is reported through a sequential aminocarbonylation/hydroformylation approach. The optimisation of palladium-catalysed aminocarbonylation of iodoaromatic substrates, using allylamine as nucleophile was first performed, with molybdenum hexacarbonyl as alternative CO source versus gaseous carbon monoxide. The combination of microwave irradiation with molybdenum hexacarbonyl allowed to selectively prepare a set of N-heterocyclic-based allylcarboxamides. Subsequent rhodium-catalysed hydroformylation of the allylcarboxamide intermediates led to the preparation of new pyridine, pyrazoline and chalcone derivatives containing both carboxamide and formyl moieties.
Organophotoredox-Mediated Amide Synthesis by Coupling Alcohol and Amine through Aerobic Oxidation of Alcohol
Samanta, Samya,Shah, Sk. Sheriff,Shee, Maniklal,Singh, Amit Kumar,Singh, N. D. Pradeep,Venkatesh, Yarra
, (2020)
The combination of an organic photocatalyst [4CzIPN (1,2,3,5-tetrakis(carbazol-9-yl)-4,6 dicyanobenzene) or 5MeOCzBN (2,3,4,5,6-pentakis(3,6-dimethoxy-9 H-carbazol-9-yl)benzonitrile)], quinuclidine, and tetra-n-butylammonium phosphate (hydrogen-bonding catalyst) was employed for amide bond formations. The hydrogen-bonded OH group activated the adjacent C?H bond of alcohols towards hydrogen atom transfer (HAT) by a radical species. The quinuclidinium radical cation, generated through single-electron oxidation of quinuclidine by the photocatalyst, employed to abstract a hydrogen atom from the α-C?H bond of alcohols selectively due to a polarity effect-produced α-hydroxyalkyl radical, which subsequently converted to the corresponding aldehyde under aerobic conditions. Then the coupling of the aldehyde and an amine formed a hemiaminal intermediate that upon photocatalytic oxidation produced the amide.
Electrogenerated superoxide anion induced oxidative amidation of benzoin
Pandolfi, Fabiana,Chiarotto, Isabella,Rocco, Daniele,Feroci, Marta
, p. 358 - 367 (2017)
Amide function is very important in both organic and medicinal chemistry. Benzamides can be obtained in good to high yields by reaction of benzoin, primary or secondary amines, molecular oxygen and electrogenerated superoxide anion (obtained with galvanos
