78-82-0Relevant articles and documents
Roles of Iron Complexes in Catalytic Radical Alkene Cross-Coupling: A Computational and Mechanistic Study
Kim, Dongyoung,Rahaman, S. M. Wahidur,Mercado, Brandon Q.,Poli, Rinaldo,Holland, Patrick L.
, p. 7473 - 7485 (2019)
A growing and useful class of alkene coupling reactions involve hydrogen atom transfer (HAT) from a metal-hydride species to an alkene to form a free radical, which is responsible for subsequent bond formation. Here, we use a combination of experimental and computational investigations to map out the mechanistic details of iron-catalyzed reductive alkene cross-coupling, an important representative of the HAT alkene reactions. We are able to explain several observations that were previously mysterious. First, the rate-limiting step in the catalytic cycle is the formation of the reactive Fe-H intermediate, elucidating the importance of the choice of reductant. Second, the success of the catalytic system is attributable to the exceptionally weak (17 kcal/mol) Fe-H bond, which performs irreversible HAT to alkenes in contrast to previous studies on isolable hydride complexes where this addition was reversible. Third, the organic radical intermediates can reversibly form organometallic species, which helps to protect the free radicals from side reactions. Fourth, the previously accepted quenching of the postcoupling radical through stepwise electron transfer/proton transfer is not as favorable as alternative mechanisms. We find that there are two feasible pathways. One uses concerted proton-coupled electron transfer (PCET) from an iron(II) ethanol complex, which is facilitated because the O-H bond dissociation free energy is lowered by 30 kcal/mol upon metal binding. In an alternative pathway, an O-bound enolate-iron(III) complex undergoes proton shuttling from an iron-bound alcohol. These kinetic, spectroscopic, and computational studies identify key organometallic species and PCET steps that control selectivity and reactivity in metal-catalyzed HAT alkene coupling, and create a firm basis for elucidation of mechanisms in the growing class of HAT alkene cross-coupling reactions.
Kinetic study of oxidation of valine by N-bromophthalimide in presence of iridium (III) chloride as homogenous catalyst
Singh, Ajaya Kumar,Jain, Bhawana,Negi, Reena,Katre, Yokraj,Singh, Surya P.,Sharma, Virender K.
, p. 71 - 77 (2010)
The mechanistic study of Ir(III) chloride catalyzed oxidation of Val has been studied by by N-bromophthalimide (NBP) in aqueous perchloric acid medium at 303 K. The reaction followed first order kinetics with respect to [NBP] and zero order kinetics with respect to [Val]. At lower concentration range of Ir(III) chloride, the reaction followed first order kinetics while tending to zero order at its higher concentration. A negative effect was observed for [H+] and [NHP] (phthalimide) whereas variation in [Hg(OAc)2] (mercuric acetate), [Cl-], ionic strength (I) and dielectric constant of the medium did not bring about any significant change on the rate of reaction. The rate constants observed at five different temperatures (298 K-318 K) were used to calculate the activation parameters. A plausible mechanism from the results of kinetic studies, reaction stoichiometry and product analysis has been proposed. Copyright Taylor & Francis Group, LLC.
Synthesis of difluoromethylselenoesters from aldehydes: Via a radical process
Guo, Rui-Li,Zhu, Xue-Qing,Zhang, Xing-Long,Wang, Yong-Qiang
supporting information, p. 8976 - 8979 (2020/08/17)
Difluoromethylselenoester compounds, another important kind of organoselenium compounds, are reported herein for the first time. They can be efficiently synthesized from aldehydes and BnSeCF2H. The synthetic method features mild reaction conditions, broad substrate scope, good tolerance of functional groups, and importantly, no metal is involved in the reaction.
Acceptorless dehydrogenation of amines to nitriles catalyzed by N-heterocyclic carbene-nitrogen-phosphine chelated bimetallic ruthenium (II) complex
Chen, Hua,Fu, Haiyan,Ji, Li,Li, Ruixiang,Nie, Xufeng,Zheng, Yanling
, p. 378 - 385 (2020/10/02)
We have developed a clean, atom-economical and environmentally friendly route for acceptorless dehydrogenation of amines to nitriles by combining a new dual N-heterocyclic carbene-nitrogen-phosphine ligand R(CNP)2 (R = o-xylyl) with a ruthenium precursor [RuCl2(η6-C6H6)]2. In this system, the electronic and steric factors of amines had a negligible influence on the reaction and a broad range of functional groups were well tolerated. All of the investigated amines could be converted to nitriles in good yield of up to 99% with excellent selectivity. The unprecedented catalytic performance of this system is attributed to the synergistic effect of two ruthenium centers chelated by R(CNP)2 and a plausible reaction mechanism is proposed according to the active species found via in situ NMR and HRMS.
NHC-catalyzed silylative dehydration of primary amides to nitriles at room temperature
Ahmed, Jasimuddin,Hota, Pradip Kumar,Maji, Subir,Mandal, Swadhin K.,Rajendran, N. M.
supporting information, p. 575 - 578 (2020/01/29)
Herein we report an abnormal N-heterocyclic carbene catalyzed dehydration of primary amides in the presence of a silane. This process bypasses the energy demanding 1,2-siloxane elimination step usually required for metal/silane catalyzed reactions. A detailed mechanistic cycle of this process has been proposed based on experimental evidence along with computational study.
Method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by Ru coordination compound
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Paragraph 0034-0039; 0255-0260, (2020/09/16)
The invention discloses a method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by a Ru coordination compound. The method comprises: adding a Ru coordination compound, an alkali, a primary amine and an organic solvent into a reaction test tube according to a mol ratio of 1:100:(100-500):1000-3000, and carrying out a stirring reaction under the condition of 80 to120 DEG C; and when gas chromatography monitors that the raw materials completely disappear, stopping the reaction, collecting the reaction solution, centrifuging the reaction solution, taking the supernatant, extracting with dichloromethane, merging the organic phases, drying, filtering, evaporating the organic solvent under reduced pressure to obtain a filtrate, and carrying out column chromatography purification on the filtrate to obtain the target product nitrile. According to the invention, the catalyst is good in activity, single in catalytic system, good in product selectivity, simple in subsequent treatment and good in system universality after the reaction is finished, has a good catalytic effect on various aryl, alkyl and heteroaryl substituted primary amines, and also has a gooddehydrogenation performance on secondary amines.
Method for continuous preparation of nitriles in a pipelined reactor (by machine translation)
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Paragraph 0036-0047; 0056; 0058, (2020/12/14)
The method comprises the following steps that a tin catalyst is coated on the inner wall of the pipeline reactor; and the method comprises the following steps: coating a tin catalyst on the inner wall of the pipeline reactor. The amide solution and the catalytic auxiliary agent are mixed and then sent to a pipeline reactor, and the amide is dehydrated to generate nitrile at the reaction pressure of 0.1 - 2.0 mpa and 100 - 200 °C reaction temperature. The resulting reaction product was separated to give the crude product of the nitrile to which the amide corresponded. In the pipeline reactor, the corresponding nitrile is continuously prepared under the action of the tin catalyst, a dehydrating agent is not needed, byproducts only are water, and three wastes are reduced. (by machine translation)
Synthesis of trifluoromethylthioesters from aldehydes: Via a visible light-promoted radical process
Guo, Rui-Li,Jia, Qiong,Wang, Meng-Yue,Wang, Yong-Qiang,Zhang, Xing-Long,Zhu, Xue-Qing
, p. 5918 - 5926 (2020/11/13)
We report herein an efficient, economical, and scalable trifluoromethylthiolation of aldehydes to generate trifluoromethylthioesters via a visible light-promoted radical process. The transformation features cheap reagents, simple operation, a broad substrate scope, and especially no metal involved in the reaction. Trifluoromethylthiolations of several complex aldehyde-containing bioactive compounds have been realized; thus the approach has the potential to be an important tool for the late-stage functionalization of advanced synthetic intermediates and bioactive molecules, and should have many applications in medicinal chemistry. This journal is
Chemical Vapor Deposition of Phase-Pure Uranium Dioxide Thin Films from Uranium(IV) Amidate Precursors
Straub, Mark D.,Leduc, Jennifer,Frank, Michael,Raauf, Aida,Lohrey, Trevor D.,Minasian, Stefan G.,Mathur, Sanjay,Arnold, John
, p. 5749 - 5753 (2019/04/16)
Homoleptic uranium(IV) amidate complexes have been synthesized and applied as single-source molecular precursors for the chemical vapor deposition of UO2 thin films. These precursors decompose by alkene elimination to give highly crystalline ph
Reductive Termination of Cyanoisopropyl Radicals by Copper(I) Complexes and Proton Donors: Organometallic Intermediates or Coupled Proton-Electron Transfer?
Thevenin, Lucas,Fliedel, Christophe,Fantin, Marco,Ribelli, Thomas G.,Matyjaszewski, Krzysztof,Poli, Rinaldo
supporting information, p. 6445 - 6457 (2019/05/15)
Cyanoisopropyl radicals, generated thermally by the decomposition of azobis(isobutyronitrile) (AIBN), participate in reductive radical termination (RRT) under the combined effect of copper(I) complexes and proton donors (water, methanol, triethylammonium salts) in acetonitrile or benzene. The investigated copper complexes were formed in situ from [CuI(MeCN)4]+BF4- in CD3CN or CuIBr in C6D6 using tris[2-(dimethylamino)ethyl]amine (Me6TREN), tris(2-pyridylmethyl)amine (TPMA), and 2,2′-bipyridine (BIPY) ligands. Upon keeping all other conditions constants, the impact of RRT is much greater for the Me6TREN and TPMA systems than for the BIPY system. RRT scales with the proton donor acidity (Et3NH+ a‰? H2O > CH3OH), it is reduced by deuteration (H2O > D2O and CH3OH > CD3OD), and it is more efficient in C6D6 than in CD3CN. The collective evidence gathered in this study excludes the intervention of an outer-sphere proton-coupled electron transfer (OS-PCET), while an inner-sphere PCET (IS-PCET) cannot be excluded for coordinating proton donors (water and methanol). On the other hand, the strong impact of RRT for the noncoordinating Et3NH+ in CD3CN results from the formation of an intermediate CuI-radical adduct, suggested by DFT calculations to involve binding via the N atom to yield keteniminato [L/Cu-N=C=CMe2]+ derivatives with only partial spin delocalization onto the Cu atom.
