25079-96-3Relevant academic research and scientific papers
Decarboxylative Ritter-Type Amination by Cooperative Iodine (I/III)─Boron Lewis Acid Catalysis
Narobe, Rok,Murugesan, Kathiravan,Schmid, Simon,K?nig, Burkhard
, p. 809 - 817 (2022/01/15)
Recent years have witnessed important progress in synthetic strategies exploiting the reactivity of carbocations via photochemical or electrochemical methods. Yet, most of the developed methods are limited in their scope to certain stabilized positions in molecules. Herein, we report a metal-free system based on the iodine (I/III) catalytic manifold, which gives access to carbenium ion intermediates also on electronically disfavored benzylic positions. The unusually high reactivity of the system stems from a complexation of iodine (III) intermediates with BF3. The synthetic utility of our decarboxylative Ritter-type amination protocol has been demonstrated by the functionalization of benzylic as well as aliphatic carboxylic acids, including late-stage modification of different pharmaceutical molecules. Notably, the amination of ketoprofen was performed on a gram scale. Detailed mechanistic investigations by kinetic analysis and control experiments suggest two mechanistic pathways.
Acetonitrile and benzonitrile as versatile amino sources in copper-catalyzed mild electrochemical C-H amidation reactions
Budnikova, Yulia,Kononov, Alexander,Rizvanov, Ildar,Strekalova, Sofia
, p. 37540 - 37543 (2021/12/07)
A mild, efficient electrochemical approach to the site-selective direct C-H amidation of benzene and its derivatives with acetonitrile and benzonitrile has been developed. It has been shown that joint electrochemical oxidation of various arenes in the presence of a copper salt as a catalyst and nitriles leads to the formation of N-phenylacetamide from benzene and N-benzylacetamides from benzyl derivatives (up to 78% yield). A favorable feature of the process is mild conditions (room temperature, ambient pressure, no strong oxidants) that meet the criteria of green chemistry.
Hydrosilylative reduction of primary amides to primary amines catalyzed by a terminal [Ni-OH] complex
Bera, Jitendra K.,Pandey, Pragati
supporting information, p. 9204 - 9207 (2021/09/20)
A terminal [Ni-OH] complex1, supported by triflamide-functionalized NHC ligands, catalyzes the hydrosilylative reduction of a range of primary amides into primary amines in good to excellent yields under base-free conditions with key functional group tolerance. Catalyst1is also effective for the reduction of a variety of tertiary and secondary amides. In contrast to literature reports, the reactivity of1towards amide reduction follows an inverse trend,i.e., 1° amide > 3° amide > 2° amide. The reaction does not follow a usual dehydration pathway.
Reductive Amidation without an External Hydrogen Source Using Rhodium on Carbon Matrix as a Catalyst
Tsygankov, Alexey A.,Makarova, Maria,Afanasyev, Oleg I.,Kashin, Alexey S.,Naumkin, Alexander V.,Loginov, Dmitry A.,Chusov, Denis
, p. 112 - 117 (2019/11/28)
An efficient method for preparation of secondary amides from primary amides and aldehydes using rhodium on carbon matrix as catalyst was developed. The method does not require any external hydrogen source and carbon monoxide is used as a reducing agent. The most active rhodium catalysts were characterized by BET, TEM and XPS techniques. Unexpectedly, it was found that heterogeneous rhodium on carbon matrix works as precatalyst for homogenous active species due to leaching of rhodium to the solution. Various secondary amides were synthesized and checked for antifungal activity. 4-Methoxy-N-(4-methoxybenzyl)benzamide demonstrated promising activity against Rhizoctonia Solani.
Environmentally benign decarboxylative: N-, O-, and S-Acetylations and acylations
Ghosh, Santanu,Purkait, Anisha,Jana, Chandan K.
supporting information, p. 8721 - 8727 (2020/12/30)
An operationally simple and general method for acetylation and acylation of a wide variety of substrates (amines, alcohols, phenols, thiols, and hydrazones) has been reported. Meldrum's acid and its derivatives have been used as an air-stable, non-volatile, cost-effective, and easy to handle acetylating/acylating agent. Easily separable byproducts (CO2 and acetone) allowed the isolation of analytically pure acetylated products without the requirement of work-up and any chromatography. This journal is
Synthesis of task-specific imidazolium ionic liquid as an efficient catalyst in acetylation of alcohols, phenols, and amines
Chaubey, Snehkrishn A.,Mishra, Roli
, p. 3259 - 3268 (2020/04/17)
Herein, we report the synthesis of task-specific amino-functionalized imidazolium ionic liquid, acetate1-(2-tert-butoxycarbonylamino-ethyl)-3-methyl-3H-imidazol-1-ium; (Boc-NH-EMIM.OAc), as an efficient catalyst for the acetylation of alcohols, phenols, and amines in the presence of acetic anhydride (acetylating reagent). Remarkably, acetic anhydride in the presence of 10?molpercent of catalyst (Boc-NH-EMIM.OAc) under solvent-free conditions showed excellent acetylation activity in shorter duration of time. On the basis of this, a general procedure for acetylation of alcohols, phenols, and amines has been developed. The ionic liquid (Boc-NH-EMIM.OAc) can be readily recovered and reused successfully up to four consecutive cycles without any significant loss of its catalytic activity. We have been able to show that this acetylating method has many advantages. It gives high yields, takes shorter time, and develops the possibility of benign environmental-friendly process.
Fe3O4@PEG core/shell nanoparticles as magnetic nanocatalyst for acetylation of amines and alcohols using ultrasound irradiations under solvent-free conditions
Veisi, Hojat,Nikseresht, Ahmad,Rostami, Afsaneh,Hemmati, Saba
, p. 507 - 520 (2018/10/24)
Abstract: Ultrasound irradiation was used to prepare one-pot Fe3O4@PEG core/shell nanostructure for the first time. The morphology, structure, and physicochemical properties were specified by different analytical techniques including field emission scanning electron microscopy, Fourier transform infrared spectroscopy, energy-dispersive X-ray spectroscopy, transmission electron microscopy, X-ray powder diffraction, and vibrating sample magnetometer. For acetylation of phenols, alcohols, and amines, the synthesized Fe3O4@PEG core/shell nanoparticles were used as an efficient heterogeneous and green catalyst with acetic anhydride under sonication applying mild reaction conditions. Different electron-withdrawing and electron-donating substrates indicate a prominent yield of desired products with the merit of reusability of Fe3O4@PEG nanocatalyst and magnetic separation. Graphical Abstract: [Figure not available: see fulltext.].
Ruthenium-Catalyzed Reductive Amidation without an External Hydrogen Source
Yagafarov, Niyaz Z.,Muratov, Karim M.,Biriukov, Klim,Usanov, Dmitry L.,Chusova, Olga,Perekalin, Dmitry S.,Chusov, Denis
supporting information, p. 557 - 563 (2018/02/09)
A catalytic reaction between aldehydes and primary amides that leads to N-alkylated amides was investigated. The developed protocol employs carbon monoxide as a deoxygenative agent and, therefore, avoids the use of an external hydrogen source. Cyclopentad
Preparation of Polydopamine Sulfamic Acid-Functionalized Silica Gel as Heterogeneous and Recyclable Nanocatalyst for Acetylation of Alcohols and Amines Under Solvent-Free Conditions
Veisi, Hojat,Vafajoo, Saba,Bahrami, Kiumars,Mozafari, Bita
, p. 2734 - 2745 (2018/07/30)
To fabricate SiO2/PDA–SO3H nanocatalyst, a suitable method is designed for the loading of sulfonic acid groups on the surface of polydopamine (PDA)-encapsulated SiO2 nanoparticles. To bridge the gap between heterogeneous and homogeneous catalysis, surface functionalization of silica gel is an elegant procedure. The morphology, structure, and physicochemical features were specified using different analytical techniques including field emission scanning electron microscopy (FESEM), Fourier transformed infrared spectroscopy (FT-IR), high resolution-transmission electron microscopy (HR-TEM), energy dispersive X-ray spectroscopy (EDS), wavelength-dispersive X-ray spectroscopy (WDX), X-ray photoelectron spectroscopy (XPS), and back titration. The SiO2/PDA–SO3H nanoparticles are efficient nanocatalysts for the acetylation of many alcohols, phenols, and amines with acetic anhydride under solvent-free conditions in good to excellent yields. Moreover, the reuse and recovery of the catalyst was shown seven times without detectible loss in activity. Graphical Abstract: [Figure not available: see fulltext.]
Transition-Metal- and Halogen-Free Oxidation of Benzylic sp 3 C-H Bonds to Carbonyl Groups Using Potassium Persulfate
Hu, Yixin,Zhou, Lihong,Lu, Wenjun
supporting information, p. 4007 - 4016 (2017/08/29)
Aryl carbonyl compounds including acetophenones, benzophenones, imides, and benzoic acids are prepared from benzyl substrates using potassium persulfate as oxidant with catalytic pyridine in acetonitrile under mild conditions. Neither transition metals nor halogens are involved in the reactions.
