10282-32-3Relevant articles and documents
d-Glucose: An Efficient Reducing Agent for a Copper(II)-Mediated Arylation of Primary Amines in Water
Bollenbach, Maud,Wagner, Patrick,Aquino, Pedro G. V.,Bourguignon, Jean-Jacques,Bihel, Frédéric,Salomé, Christophe,Schmitt, Martine
, p. 3244 - 3249 (2016)
A copper-catalyzed Ullmann-type amination with primary amines in water with a combination of copper(II) triflate [Cu(OTf)2], dipivaloylmethane, and d-glucose is reported. The mild conditions and the use of an inexpensive catalyst as well as a renewable feedstock (d-glucose and the surfactant TPGS-750-M, which is derived from vitamin E) make this protocol a safe and convenient strategy for efficient C?N bond formation. This easy-to-handle procedure is extremely competitive compared to palladium-based reactions and may be used to synthesize N-containing molecules, such as drugs or organic light-emitting diodes (OLEDs).
Mechanistic investigation of the iridium-catalysed alkylation of amines with alcohols
Fristrup, Peter,Tursky, Matyas,Madsen, Robert
, p. 2569 - 2577 (2012)
The [Cp*IrCl2]2-catalysed alkylation of amines with alcohols was investigated using a combination of experimental and theoretical methods. A Hammett study involving a series of para-substituted benzyl alcohols resulted in a line with a negative slope. This clearly documents that a positive charge is built up in the transition state, which in combination with the measurement of a significant kinetic isotope effect determines hydride abstraction as being the selectivity-determining step under these conditions. A complementary Hammett study using para-substituted anilines was also carried out. Again, a line with a negative slope was obtained suggesting that nucleophilic attack on the aldehyde is selectivity-determining. A computational investigation of the entire catalytic cycle with full-sized ligands and substrates was performed using density functional theory. The results suggest a catalytic cycle where the intermediate aldehyde stays coordinated to the iridium catalyst and reacts with the amine to give a hemiaminal which is also bound to the catalyst. Dehydration to the imine and reduction to the product amine also takes place without breaking the coordination to the catalyst. The fact that the entire catalytic cycle takes place with all the intermediates bound to the catalyst is important for the further development of this synthetic transformation. The Royal Society of Chemistry 2012.
Heterogeneous cobalt catalysts for reductive amination with H2: General synthesis of secondary and tertiary amines
Mao, Fei,Sui, Dejun,Qi, Zhengliang,Fan, Haipeng,Chen, Rizhi,Huang, Jun
, p. 94068 - 94073 (2016)
Heterogeneous Co@NC catalysts were prepared, characterized and applied for the reductive amination of aldehydes and ketones with H2 gas. The Co catalyst Co@NC (800-2 h) was found to be active and selective for the reductive amination of aldehydes and ketones using H2 gas. Thus, general synthesis of secondary and tertiary amines was developed by the Co-catalyzed reductive amination with H2 gas, and various secondary and tertiary amines can be obtained in high yields. Moreover, a practical synthesis of N-substituted isoindolinones was also presented by a one step process with the Co@NC (800-2 h) catalyst. The Co@NC (800-2 h) catalyst is reusable at least five times without evident loss of activity.
Amination of alcohols catalyzed by copper-aluminium Hydrotalcite: A green synthesis of amines
Likhar, Pravin R.,Arundhathi, Racha,Kantam, Mannepalli Lakshmi,Prathima, Parvathaneni Sai
, p. 5383 - 5389 (2009)
Copper-aluminium hydrotalcite (CuAl-HT)/K2CO3 has been employed in the activation of various benzyl alcohols with benzylamines to afford the corresponding amines in good to high yields. Experimentation showed that the reaction takes place through sequential transformations: the oxidation of alcohols into carbonyl compounds, imine formation between amines and carbonyl compounds, and then reduction of imines to amines, heterogeneously catalyzed by non-noble Cu-Al HT catalyst in a one-pot and straightforward fashion. The process was further extended to amination of alcohols with anilines, which are often resistant to alkylation reactions when substituted with strong electron-withdrawing groups.
Intramolecular nucleophilic aromatic substitution reaction of 2-carboxamido-3-arylquinazolin-4-ones and its application to the synthesis of secondary aryl amines
Fuwa, Haruhiko,Kobayashi, Toshitake,Tokitoh, Takashi,Torii, Yukiko,Natsugari, Hideaki
, p. 2497 - 2500 (2004)
A novel intramolecular nucleophilic aromatic substitution reaction of 2-carboxamido-3-arylquinazolin-4-one derivatives induced by base treatment and its application to the expeditious synthesis of secondary aryl amines, including diaryl amines, are descri
New Insights into the Reaction Capabilities of Ionic Organic Bases in Cu-Catalyzed Amination
Lo, Quintin A.,Sale, David,Braddock, D. Christopher,Davies, Robert P.
, p. 1944 - 1951 (2019)
The application of ionic organic bases in the copper-catalyzed amination reaction (Ullmann reaction) has been studied at room temperature, with sub-mol-% catalyst loadings, and with more challenging amines at elevated temperatures. The cation present in the base has been shown to have little effect on the reaction at standard catalyst and ancillary ligand loadings, whereas the choice of anion is crucial for good reactivity. A substrate scope carried out at room temperature with the best performing bases, TBAM and TBPM, showed both bases to be highly effective under these mild reaction conditions. Moreover, under sub-mol % catalyst loadings and room temperature conditions, TBPM gave good to excellent yields for a number of different amines and functionalized aryl iodides (14 examples). However, reactions involving more challenging amines gave little or no yield. By using more forceful conditions (120 °C) moderate to excellent yields of cross-coupled products containing more challenging amines was achievable using TBPM and to a lesser extent with TBAM. As part of this work a study on the stability of the organic bases at 120 °C was undertaken. TBAM is shown to decompose to give nBu3N and mono-butylmalonate at higher temperatures, and this can be correlated to a decrease in performance in the coupling reaction. The phosphonium cations in TBPM did not undergo analogous reactivity but were shown instead to experience some degree of deprotonation at the α-CH2 to generate phosphonium ylides. This however did not lead to a significantly degradation in the activity of the TBPM in the cross-coupling reaction.
One-pot Reductive Amination of carbonyl Compounds with Nitro Compounds by Transfer Hydrogenation over Co–Nx as catalyst
Zhou, Peng,Zhang, Zehui
, p. 1892 - 1897 (2017)
A new method was developed for the synthesis of secondary amines through the one-pot reductive amination of carbonyl compounds with nitro compounds using formic acid as the hydrogen donor over a heterogeneous non-noble-metal catalyst (Co-Nx/C-800-AT, generated by the pyrolysis of the cobalt phthalocyanine/silica composite at 800°C under a N2 atmosphere and subsequent etching by HF). Both nitrogen and cobalt were of considerable importance in the transfer hydrogenation reactions with formic acid.
Electrophilic Activation of [1.1.1]Propellane for the Synthesis of Nitrogen-Substituted Bicyclo[1.1.1]pentanes
A?ssa, Christophe,Duarte, Fernanda,Goundry, William R. F.,Livesley, Sarah,Morris, James A.,Robertson, Craig M.,Sterling, Alistair J.
supporting information, (2021/11/30)
Strategies commonly used for the synthesis of functionalised bicyclo[1.1.1]pentanes (BCP) rely on the reaction of [1.1.1]propellane with anionic or radical intermediates. In contrast, electrophilic activation has remained a considerable challenge due to t
Iron-Catalyzed Oxidative Amination of Benzylic C(sp3)–H Bonds with Anilines
Song, Yan-Ling,Li, Bei,Xie, Zhen-Biao,Wang, Dan,Sun, Hong-Mei
supporting information, p. 17975 - 17985 (2021/12/13)
Iron-catalyzed oxidative amination of benzylic C(sp3)–H bonds with anilines bearing electron-withdrawing groups (EWGs) or electron-donating groups (EDGs) is realized based on simple variations of N-substituents on imidazolium cations in novel ionic Fe(III) complexes. The structural modification of the imidazolium cation resulted in regulation of the redox potential and the catalytic performance of the iron metal center. Using DTBP as oxidant, [HItBu][FeBr4] showed the highest catalytic activity for anilines bearing EWGs, while [HIPym][FeBr4] was more efficient for EDG-substituted anilines. This work provides alternative access to benzylamines with the advantages of both a wide substrate scope and iron catalysis.
