492-85-3Relevant academic research and scientific papers
Direct Amidation of Esters by Ball Milling**
Barreteau, Fabien,Battilocchio, Claudio,Browne, Duncan L.,Godineau, Edouard,Leitch, Jamie A.,Nicholson, William I.,Payne, Riley,Priestley, Ian
supporting information, p. 21868 - 21874 (2021/09/02)
The direct mechanochemical amidation of esters by ball milling is described. The operationally simple procedure requires an ester, an amine, and substoichiometric KOtBu and was used to prepare a large and diverse library of 78 amide structures with modest to excellent efficiency. Heteroaromatic and heterocyclic components are specifically shown to be amenable to this mechanochemical protocol. This direct synthesis platform has been applied to the synthesis of active pharmaceutical ingredients (APIs) and agrochemicals as well as the gram-scale synthesis of an active pharmaceutical, all in the absence of a reaction solvent.
Manganese Catalyzed Direct Amidation of Esters with Amines
Fu, Zhengqiang,Wang, Xinghua,Tao, Sheng,Bu, Qingqing,Wei, Donghui,Liu, Ning
, p. 2339 - 2358 (2021/02/03)
The transition metal catalyzed amide bond forming reaction of esters with amines has been developed as an advanced approach for overcoming the shortcomings of traditional methods. The broad scope of substrates in transition metal catalyzed amidations remains a challenge. Here, a manganese(I)-catalyzed method for the direct synthesis of amides from a various number of esters and amines is reported with unprecedented substrate scope using a low catalyst loading. A wide range of aromatic, aliphatic, and heterocyclic esters, even in fatty acid esters, reacted with a diverse range of primary aryl amines, primary alkyl amines, and secondary alkyl amines to form amides. It is noteworthy that this approach provides the first example of the transition metal catalyzed amide bond forming reaction from fatty acid esters and amines. The acid-base mechanism for the manganese(I)-catalyzed direct amidation of esters with amines was elucidated by DFT calculations.
Nickel-Catalyzed Amide Bond Formation from Methyl Esters
Ben Halima, Taoufik,Masson-Makdissi, Jeanne,Newman, Stephen G.
supporting information, p. 12925 - 12929 (2018/09/14)
Despite being one of the most important and frequently run chemical reactions, the synthesis of amide bonds is accomplished primarily by wasteful methods that proceed by stoichiometric activation of one of the starting materials. We report a nickel-catalyzed procedure that can enable diverse amides to be synthesized from abundant methyl ester starting materials, producing only volatile alcohol as a stoichiometric waste product. In contrast to acid- and base-mediated amidations, the reaction is proposed to proceed by a neutral cross coupling-type mechanism, opening up new opportunities for direct, efficient, chemoselective synthesis.
Base-Controlled Completely Selective Linear or Branched Rhodium(I)-Catalyzed C?H ortho-Alkylation of Azines without Preactivation
Tran, Ga?l,Hesp, Kevin D.,Mascitti, Vincent,Ellman, Jonathan A.
supporting information, p. 5899 - 5903 (2017/05/12)
A [RhI]/bisphosphine/base catalytic system for the ortho-selective C?H alkylation of azines by acrylates and acrylamides is reported. This catalytic system features an unprecedented complete linear or branched selectivity that is solely dependent on the catalytic base that is used. Complete branched selectivity is even achieved for ethyl methacrylate, which enables the introduction of a quaternary carbon center. Excellent functional group compatibility is demonstrated for both linear and branched alkylations. The operational simplicity and broad scope of this transformation allow for rapid access to functionalized azines of direct pharmaceutical and agrochemical relevance.
Copper-Catalyzed Aerobic Oxidative Amidation of Benzyl Alcohols
Krabbe, Scott W.,Chan, Vincent S.,Franczyk, Thaddeus S.,Shekhar, Shashank,Napolitano, José G.,Presto, Carmina A.,Simanis, Justin A.
, p. 10688 - 10697 (2016/11/29)
A Cu-catalyzed synthesis of amides from alcohols and secondary amines using the oxygen in air as the terminal oxidant has been developed. The methodology is operationally simple requiring no high pressure equipment or handling of pure oxygen. The commercially available, nonprecious metal catalyst, Cu(phen)Cl2, in conjunction with di-tert-butyl hydrazine dicarboxylate and an inorganic base provides a variety of benzamides in moderate to excellent yields. The pKa of amine conjugate acid and electronics of alcohol were shown to impact the selection of base for optimal reactivity. A mechanism consistent with the observed reactivity trends, KIE, and Hammett study is proposed.
Photoinduced Aminocarbonylation of Aryl Iodides
Kawamoto, Takuji,Sato, Aoi,Ryu, Ilhyong
supporting information, p. 14764 - 14767 (2015/10/19)
Transition metal-catalyzed aminocarbonylation of aryl halides with CO and amines, pioneered by Heck and co-workers in the 1970s, is among the most commonly employed reactions to make aromatic amides. A catalyst-free aminocarbonylation of aryl iodides with CO and amines, which simply uses photoirradiation conditions by Xe-lamp, has now been developed. This methodology shows broad functional-group tolerance, including that of heteroaromatic amides. A hybrid radical/ionic chain mechanism, involving electron transfer from zwitterionic radical intermediates generated by nucleophilic attack of amines to aroyl radicals, is proposed.
Novel methanone derivatives, preparation method thereof, and pharmaceutical composition for use in preventing or treating blindness related diseases containing the same as an active ingredient
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Paragraph 0130-0132, (2016/10/10)
The present invention relates to novel methanone derivatives, a preparation method thereof, and a pharmaceutical composition comprising the same as an active ingredient for preventing or treating retinal diseases. Since the novel methanone derivatives according to the present invention, optical isomers thereof or pharmaceutically acceptable salts thereof have an excellent effect of inhibiting receptor-interacting serine/threonine-protein kinase 1 (RIPK1), the composition comprising the same as an active ingredient can be advantageously used as a pharmaceutical composition for preventing or treating retinal diseases such as retinitis pigmentosa (RP), Leberandprime;s congenital amaurosis (LCA), Stargardts disease, Usher syndrome, choroideremia, rod-cone or cone-rod dystrophy, ciliopathies, a mitochondrial disorder, progressive retinal atrophy, a degenerative retinal disease, age-related macular degeneration (AMD), wet AMD, dry AMD, geographic atrophy, hereditary or acquired maculopathy, a retinal photoreceptor disease, a retinal pigment epithelial disease, diabetic retinopathy, cystic macular edema, uveitis, retinal detachment, traumatic retinal damage, iatrogenic retinal damage, a macular hole, macular capillary ectasia, a ganglion cell disease, an optic nerve disease, glaucoma, optic neuropathy, ischemic retinal disease , retinopathy of prematurity (ROP), retinal vascular occlusion, hereditary macroaneurysm, a retinal vascular disease , an ophthalmovascular disease, degeneration of retinal neuronal cells caused by glaucoma, or ischemic optic neuropathy.COPYRIGHT KIPO 2015
Chloroform as a Carbon Monoxide Precursor: In or Ex Situ Generation of CO for Pd-Catalyzed Aminocarbonylations
Gockel, Samuel N.,Hull, Kami L.
supporting information, p. 3236 - 3239 (2015/07/15)
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).
Co2(CO)8 as a convenient in situ CO source for the direct synthesis of benzamides from aryl halides (Br/I) via aminocarbonylation
Baburajan, Poongavanam,Elango, Kuppanagounder P.
supporting information, p. 1006 - 1010 (2014/02/14)
A fast, mild, and functional group tolerant method for the direct synthesis of benzamides from aryl halides (Br, I) via aminocarbonylation, using solid Co2(CO)8 as a convenient CO source, has been demonstrated. The developed method is applicable to a wide variety of 1 and cyclic and acyclic 2 amines. Nitro substituted (o, m and p) aryl halides have easily been converted to the corresponding benzamides, without the reduction of the nitro group, in high yields using this in situ carbonylation methodology under microwave irradiation.
Co2(CO)8 as a convenient in situ CO source for the direct synthesis of benzamides from aryl halides (Br/I) via aminocarbonylation
Baburajan, Poongavanam,Elango, Kuppanagounder P.
supporting information, p. 1006 - 1010 (2015/02/19)
A fast, mild, and functional group tolerant method for the direct synthesis of benzamides from aryl halides (Br, I) via aminocarbonylation, using solid Co2(CO)8 as a convenient CO source, has been demonstrated. The developed method is applicable to a wide variety of 1° and cyclic and acyclic 2°amines. Nitro substituted (o, m and p) aryl halides have easily been converted to the corresponding benzamides, without the reduction of the nitro group, in high yields using this in situ carbonylation methodology under microwave irradiation.
