6321-12-6Relevant academic research and scientific papers
Hydration of Aliphatic Nitriles Catalyzed by an Osmium Polyhydride: Evidence for an Alternative Mechanism
Babón, Juan C.,Esteruelas, Miguel A.,López, Ana M.,O?ate, Enrique
, p. 7284 - 7296 (2021/05/29)
The hexahydride OsH6(PiPr3)2 competently catalyzes the hydration of aliphatic nitriles to amides. The main metal species under the catalytic conditions are the trihydride osmium(IV) amidate derivatives OsH3{κ2-N,O-[HNC(O)R]}(PiPr3)2, which have been isolated and fully characterized for R = iPr and tBu. The rate of hydration is proportional to the concentrations of the catalyst precursor, nitrile, and water. When these experimental findings and density functional theory calculations are combined, the mechanism of catalysis has been established. Complexes OsH3{κ2-N,O-[HNC(O)R]}(PiPr3)2 dissociate the carbonyl group of the chelate to afford κ1-N-amidate derivatives, which coordinate the nitrile. The subsequent attack of an external water molecule to both the C(sp) atom of the nitrile and the N atom of the amidate affords the amide and regenerates the κ1-N-amidate catalysts. The attack is concerted and takes place through a cyclic six-membered transition state, which involves Cnitrile···O-H···Namidate interactions. Before the attack, the free carbonyl group of the κ1-N-amidate ligand fixes the water molecule in the vicinity of the C(sp) atom of the nitrile.
Aerobic oxidation of primary amines to amides catalyzed by an annulated mesoionic carbene (MIC) stabilized Ru complex
Yadav, Suman,Reshi, Noor U Din,Pal, Saikat,Bera, Jitendra K.
, p. 7018 - 7028 (2021/11/17)
Catalytic aerobic oxidation of primary amines to the amides, using the precatalyst [Ru(COD)(L1)Br2] (1) bearing an annulated π-conjugated imidazo[1,2-a][1,8]naphthyridine-based mesoionic carbene ligand L1, is disclosed. This catalytic protocol is distinguished by its high activity and selectivity, wide substrate scope and modest reaction conditions. A variety of primary amines, RCH2NH2 (R = aliphatic, aromatic and heteroaromatic), are converted to the corresponding amides using ambient air as an oxidant in the presence of a sub-stoichiometric amount of KOtBu in tBuOH. A set of control experiments, Hammett relationships, kinetic studies and DFT calculations are undertaken to divulge mechanistic details of the amine oxidation using 1. The catalytic reaction involves abstraction of two amine protons and two benzylic hydrogen atoms of the metal-bound primary amine by the oxo and hydroxo ligands, respectively. A β-hydride transfer step for the benzylic C-H bond cleavage is not supported by Hammett studies. The nitrile generated by the catalytic oxidation undergoes hydration to afford the amide as the final product. This journal is
Development and Utilization of a Palladium-Catalyzed Dehydration of Primary Amides to Form Nitriles
Al-Huniti, Mohammed H.,Rivera-Chávez, José,Colón, Katsuya L.,Stanley, Jarrod L.,Burdette, Joanna E.,Pearce, Cedric J.,Oberlies, Nicholas H.,Croatt, Mitchell P.
supporting information, p. 6046 - 6050 (2018/09/27)
A palladium(II) catalyst, in the presence of Selectfluor, enables the efficient and chemoselective transformation of primary amides into nitriles. The amides can be attached to aromatic rings, heteroaromatic rings, or aliphatic side chains, and the reactions tolerate steric bulk and electronic modification. Dehydration of a peptaibol containing three glutamine groups afforded structure-activity relationships for each glutamine residue. Thus, this dehydration can act similarly to an alanine scan for glutamines via synthetic mutation.
TARGETED PEPTIDE CONJUGATES
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Paragraph 0238; 0239, (2018/08/12)
The present invention relates to the preparation and use of therapeutic compounds for the treatment of diseases at specific subcellular target areas such as specific cellular organelles. In particular, the therapeutic compounds of the invention are specific for modifying enzyme activity within targeted organelles or structures of cells and tissues. Subcellular organelles and structures that may be specifically targeted by compounds of the present invention include lysosomes, autophagasomes, the endoplasmic reticulum, the Golgi complex, peroxisomes, the nucleus, membranes and the mitochondria.
Sodium azide as a catalyst for the hydration of nitriles to primary amides in water
Bahrami, Kiumars,Khodaei, Mohammad Mehdi,Roostaei, Mohsen
, p. 267 - 269 (2015/06/02)
The selective conversion of aromatic nitriles to primary amides has been accomplished using sodium azide. The corresponding amides were obtained efficiently in excellent yields. This reaction was carried out under eco-friendly conditions using water in the absence of organic solvents.
Chemoselective hydration of nitriles to amides using hydrated ionic liquid (IL) tetrabutylammonium hydroxide (TBAH) as a green catalyst
Veisi, Hojat,Maleki, Behrooz,Hamelian, Mona,Ashrafi, Samaneh Sedigh
, p. 6365 - 6371 (2015/02/19)
A transition metal-free process, catalyzed by tetrabutylammonium hydroxide (TBAH), has been developed for the convenient and selective hydration of nitriles to the corresponding amides. The present process converts aromatic, aliphatic, and heteroaromatic nitriles with a wide variety of functional groups into amides. The regioselective hydration of one nitrile moiety in the presence of another nitrile group gives the present protocol high impact.
Synthesis of Nitriles from Aldoximes and Primary Amides Using XtalFluor-E
Keita, Massaba,Vandamme, Mathilde,Paquin, Jean-Fran?ois
, p. 3758 - 3766 (2015/11/28)
The dehydration reaction of aldoximes and amides for the synthesis of nitriles using [Et2NSF2]BF4 (XtalFluor-E) is described. Overall, the reaction proceeds rapidly (normally 1 h) at room temperature in an environmentally benign solvent (EtOAc) with only a slight excess of the dehydrating agent (1.1 equiv). A broad scope of nitriles can be prepared, including chiral nonracemic ones. In addition, in a number of cases, further purification of the nitrile after the workup was not required.
HETEROAROMATIC DERIVATIVES AND PHARMACEUTICAL APPLICATIONS THEREOF
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Paragraph 00701, (2015/11/10)
Provided herein are novel heteroaromatic derivatives, or a stereoisomer, a geometric isomer, a tautomer, an N-oxide, a hydrate, a solvate, a prodrug, a pharmaceutically acceptable salt or a prodrug thereof, and pharmaceutical compositions containing such compounds. Also provided herein are uses of such compounds or pharmaceutical compositions thereof in the manufacture of a medicament for treating respiratory diseases, especially chronic obstructive pulmonary disease (COPD).
AZAQUINAZOLINE INHIBITORS OF ATYPICAL PROTEIN KINASE C
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Page/Page column 349, (2014/04/17)
The present invention provides a compound of formula (I) or a salt thereof, wherein R7, R8, R9, G, and X are as defined herein. A compound of formula (I) and its salts have a PKC inhibitory activity, and may be used to treat proliferative disorders.
An efficient hydration of nitriles to amides in aqueous media by hydrotalcite-clay supported nickel nanoparticles
Subramanian, Thirumeni,Pitchumani, Kasi
, p. 109 - 113 (2013/01/15)
Hydrotalcite-clay supported nickel nanoparticles catalyze hydration of nitriles to amides in aqueous media. This Ni NPs/HT system is efficient for the synthesis of a diverse range of amides and affords the expected products with good yields in aqueous media. The synthesized nickel nanoparticles are characterized by UV-DRS, powder XRD, SEM and HRTEM. The catalyst is reused at least three times and a plausible mechanism is proposed. This fast, simple, effective and environmentally benign heterogeneous protocol provides a safer alternative to hazardous, corrosive and more polluting conventional catalysts.
