5331-48-6Relevant academic research and scientific papers
Pillar[5]arenes with an introverted amino group: A hydrogen bonding tuning effect
Chen, Lei,Li, Zhiming,Chen, Zhenxia,Hou, Jun-Li
, p. 248 - 251 (2013)
Pillar[5]arenes with introverted amino groups were produced through aminolysis. X-ray analysis demonstrated that the intramolecular hydrogen bonding induced the amino group toward the inner space of the cavity. The kinetic studies and molecular modelings revealed that the hydrogen bonding also contributed to the acceleration of the aminolysis through stabilizing the intermediate.
An NMR study on a pseudo-intramolecular transacylation reaction of an α-aryl-β-keto ester
Hirai, Sho,Asahara, Haruyasu,Hirao, Shotaro,Sawayama, Jun,Sugimoto, Ryuichi,Saigo, Kazuhiko,Nishiwaki, Nagatoshi
, p. 4889 - 4892 (2014)
The pseudo-intramolecular transacylation reaction efficiently proceeds like an intramolecular reaction, even though it is actually an intermolecular reaction. We have obtained valuable insights by monitoring the reaction by 1H NMR spectroscopy.
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.
Monoacylation of Symmetrical Diamines in Charge Microdroplets
Ansu-Gyeabourh, Emelia,Amoah, Enoch,Ganesa, Chandrashekar,Badu-Tawiah, Abraham K.
, p. 531 - 536 (2021/01/13)
Monoacylation of symmetrical diamine is achieved when the primary α,ω-diamines (carbon numbers n = 3, 5 and 12) are diluted in ethyl acetate, and the resultant mixture is electrosprayed across a 10 mm distance in ambient air toward a mass spectrometer. The N-acylated product is formed in charged microdroplets without acidifying and activating agents and in the absence of heat. This result provided an insight into the orientation of the amines in the droplets, suggesting that the ester is activated to react with the amine at the droplet surface due to the high abundance of protons at the air-droplet interface.
A novel construction of acetamides from rhodium-catalyzed aminocarbonylation of DMC with nitro compounds
Bao, Zhi-Peng,Miao, Ren-Guan,Qi, Xinxin,Wu, Xiao-Feng
supporting information, p. 1955 - 1958 (2021/03/02)
Dimethyl carbonate (DMC), an environment-friendly compound prepared from CO2, shows diverse reactivities. In this communication, an efficient procedure using DMC as both a C1 building block and solvent in the aminocarbonylation reaction with nitro compounds has been developed. W(CO)6acts both a CO source and a reductant here.
PRODUCTION METHOD OF AMIDE COMPOUND
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Paragraph 0018; 0089-0106, (2020/10/08)
PROBLEM TO BE SOLVED: To provide a production method of an amide compound, which can use a variety of carboxylic acid halides and can produce a desired amide compound at a yield higher than a batch process by suppressing a side reaction. SOLUTION: Provided is a production method of an amide compound using a flow type reactor, in which the flow type reactor includes: a first flow path; a second flow path; a first mixing means provided at a confluent part of the first flow path and the second flow path; and a third flow path that is connected to the first mixing means and arranged on a down stream side of the first mixing means, the production method comprising: a mixing step of obtaining a mixed liquid by circulating a first liquid containing the carboxylic acid halide in the first flow path, circulating a second liquid containing an amine compound having a molecular weight of 1,000 or less, an inorganic alkali and water in the second flow path, and mixing the first liquid and the second liquid by the first mixing means to obtain a mixture; and a reaction step of obtaining an amide compound by circulating the mixed liquid in the third flow path and reacting the carboxylic acid halide and the amine compound in the third flow path. SELECTED DRAWING: Figure 1 COPYRIGHT: (C)2020,JPO&INPIT
Synthesis of diverse libraries of carboxamides via chemoselective N-acylation of amines by carboxylic acids employing Br?nsted acidic IL [BMIM(SO3H)][OTf]
Savanur, Hemantkumar M.,Malunavar, Shruti S.,Prabhala, Pavankumar,Sutar, Suraj M.,Kalkhambkar, Rajesh G.,Laali, Kenneth K.
supporting information, (2019/09/30)
Chemoselective N-acylation of amines with carboxylic acids as acyl electrophiles and Br?nsted acidic IL [BMIM(SO3H)][OTf] as promoter is reported under both thermal and microwave irradiation to produce libraries of carboxamides in good to excellent yields after a simple workup. The protocol is compatible with structurally diverse 1° and 2° amines and works in the presence of sensitive functional groups such as thiols and phenols. The potential for recycling and reuse of the IL is also demonstrated.
Metal-Free O-Selective Direct Acylation of Amino Alcohols Through Pseudo-Intramolecular Process
Yokoyama, Soichi,Shibauchi, Hiroshi,Asahara, Haruyasu,Nishiwaki, Nagatoshi
supporting information, p. 1125 - 1133 (2019/02/01)
Efficient α-aryl-β-keto ester acylation of amine accompanied by the elimination of ethyl phenylacetate was achieved owing to the pseudo-intramolecular process. The eliminated ethyl phenylacetate could be recycled by conversion into an α-aryl-β-keto ester upon treatment with an acyl chloride in the presence of lithium bis(trimethylsilyl)amide, by which the atom economy considerably increased. Acylation using an α-aryl-β-keto ester is highly sensitive to the bulkiness of the nucleophile, which facilitated the regioselective-acylation of the less hindered amino group in diamine without protecting the other. The transacylation of α-aryl-β-keto ester with N-alkylamino alcohol resulted in chemoselective O-acylation without protecting the amino group because the hydroxy group was attracted to the reaction site of the keto ester by forming an ammonium salt. Transacylation was demonstrated to be a practically useful tool for organic synthesis because this protocol can be conducted under mild conditions with simple manipulations in the absence of any additives such as metal catalyst and base.
Efficient acylation and transesterification catalyzed by dilithium tetra-tert-butylzincate at low temperatures
Oshimura, Miyuki,Oda, Yuki,Kondoh, Keita,Hirano, Tomohiro,Ute, Koichi
, p. 2070 - 2073 (2016/04/26)
The acylation and transesterification of alcohols with vinyl acetate and carboxylic esters were investigated in the presence of a catalytic amount (1-10 mol %) of dilithium tetra-tert-butylzincate (TBZL) as a catalyst. The acylation proceeded quantitatively at 0 °C within 1 h. The transesterification occurred for a wide range of combinations of esters and alcohols at 0 to -40 °C. To the best of our knowledge, this is the first successful transesterification at such low temperatures. The time-conversion plots for the transesterification show that the reaction reached equilibrium within 5 min at 0 °C. The reaction proceeded quantitatively by addition of molecular sieves 4A. In addition, the transesterification proceeded even in the presence of H2O and amines.
Carboxyl activation of 2-mercapto-4,6-dimethylpyrimidine through n-acyl-4,6-dimethylpyrimidine-2-thione: A chemical and spectrophotometric investigation
Rajan
, p. 287 - 291 (2015/01/30)
2-Mercapto-4,6-dimethylpyrimidine, as effective carboxyl activating group, has been successfully proved by converting it into respective acyl derivatives and the subsequent conversion to the amides and esters respectively using amines, amino alcohols and alcohols. The aminolysis and esterification were monitored chemically and spectrophotometrically. This paved way to establish that the above mercaptopyrimidine derivative is an efficient carboxyl activating group applicable in solid phase peptide synthesis.
