98393-39-6Relevant articles and documents
Homologation of α-aryl amino acids through quinone-catalyzed decarboxylation/Mukaiyama-Mannich addition
Haugeberg, Benjamin J.,Phan, Johnny H.,Liu, Xinyun,O'Connor, Thomas J.,Clift, Michael D.
, p. 3062 - 3065 (2017)
A new method for amino acid homologation by way of formal C-C bond functionalization is reported. This method utilizes a 2-step/1-pot protocol to convert α-amino acids to their corresponding N-protected β-amino esters through quinone-catalyzed oxidative decarboxylation/in situ Mukaiyama-Mannich addition. The scope and limitations of this chemistry are presented. This methodology provides an alternative to the classical Arndt-Eistert homologation for accessing β-amino acid derivatives. The resulting N-protected amine products can be easily deprotected to afford the corresponding free amines.
Identification of N-acyl-N-indanyl-α-phenylglycinamides as selective TRPM8 antagonists designed to mitigate the risk of adverse effects
Kobayashi, Jun-ichi,Hirasawa, Hideaki,Fujimori, Yoshikazu,Nakanishi, Osamu,Kamada, Noboru,Ikeda, Tetsuya,Yamamoto, Akitoshi,Kanbe, Hiroki
, (2020/12/21)
Transient receptor potential melastatin 8 (TRPM8), a temperature-sensitive ion channel responsible for detecting cold, is an attractive molecular target for the treatment of pain and other disorders. We have previously discovered a selective TRPM8 antagon
Synthesis of limonene β-amino alcohol from (R)-(+)-α-methylbenzylamine and (+)-limonene 1,2-epoxide
Ait Said, Lyazid,El Bachiri, Abdelhadi,El Haimer, Chaimaa,El Hammoumi, Mohamed Merouane,Khoukhi, Mostafa
, (2021/06/02)
Two new compounds of β-amino alcohol are obtained using (R) - (+) - α-methylbenzylamine as starting material which is converted into two amines. Each of these compounds reacted in excess with a 1: 1 mixture of cis and trans-limonene oxide in the presence of water as a catalyst. The products obtained show that β-amino alcohol derived from trans-limonene oxide is obtained and unreacted cis-limonene oxide from the reaction mixture as well as the amine is attained. Whereas the addition of the synthesized carbamate of the same primary amine over the 1: 1 mixture of cis and trans -limonene oxide in the presence of water results in the hydrolysis product and the recovery of unreacted trans-limonene oxide.
Manganese-Catalyzed Selective Hydrogenative Cross-Coupling of Nitriles and Amines to Form Secondary Imines
Li, Xiao-Gen,Zhou, Qi-Lin
supporting information, p. 3471 - 3475 (2021/04/29)
Manganese complexes with tridentate PNN ligands have been synthesized as catalysts for hydrogenative cross-coupling reaction of nitriles and amines to form secondary imines. This reaction afforded a variety of unsymmetrical secondary imines in good yields with excellent selectivity. Investigation of catalyst intermediates indicated that an amido manganese complex may be the active catalyst species for this reaction. (Figure presented.).
Vanadium-and chromium-catalyzed dehydrogenative synthesis of imines from alcohols and amines
Madsen, Robert,Miao, Yulong,Samuelsen, Simone V.
supporting information, p. 1328 - 1335 (2021/05/29)
Vanadium(IV) tetraphenylporphyrin dichloride and chromium(III) tetraphenylporphyrin chloride have been developed as catalysts for the acceptorless dehydrogenation of alcohols. The catalysts have been applied to the direct synthesis of imines in overall good yields from a variety of alcohols and amines. The transformations are proposed to proceed by metal?ligand bifunctional pathways with an outer-sphere transfer of two hydrogen atoms from the alcohol to the metal porphyrin complexes. The results show that vanadium and chromium catalysts can also be employed for the dehydrogenation of alcohols with the release of hydrogen gas, and they may represent valuable alternatives to other catalysts based on Earth-abundant metals.
Sulfur-stabilised copper nanoparticles for the aerobic oxidation of amines to imines under ambient conditions
Martín-García, Iris,Díaz-Reyes, Gloria,Sloan, George,Moglie, Yanina,Alonso, Francisco
supporting information, p. 11312 - 11322 (2021/05/19)
The stabilisation of metal nanoparticles and control of their oxidation state are crucial factors in nanocatalysis. Elemental sulfur has been found to be a cheap and effective stabilising agent for copper nanoparticles in the form of copper(i) oxide. The
Dehydrogenative amide synthesis from alcohols and amines utilizing N-heterocyclic carbene-based ruthenium complexes as efficient catalysts: The influence of catalyst loadings, ancillary and added ligands
Wang, Wan-Qiang,Wang, Zhi-Qin,Sang, Wei,Zhang, Rui,Cheng, Hua,Chen, Cheng,Peng, Da-Yong
supporting information, (2021/01/05)
The metal-catalyzed dehydrogenative coupling of alcohols and amines to access amides has been recognized as an atom-economic and environmental-friendly process. Apart from the formation of the amide products, three other kinds of compounds (esters, imines and amines) may also be produced. Therefore, it is of vital importance to investigate product distribution in this transformation. Herein, N-heterocyclic carbene-based Ru (NHC/Ru) complexes [Ru-1]-[Ru-5] with different ancillary ligands were prepared and characterized. Based on these complexes, we selected condition A (without an added NHC precursor) and condition B (with an added NHC precursor) to comprehensively explore the selectivity and yield of the desired amides. After careful evaluation of various parameters, the Ru loadings, added NHC precursors and the electronic/steric properties of ancillary NHC ligands were found to have considerable influence on this catalytic process.
Stereochemical analysis of chiral amines, diamines, and amino alcohols: Practical chiroptical sensing based on dynamic covalent chemistry
Hassan, Diandra S.,Thanzeel, F. Yushra,Wolf, Christian
supporting information, p. 457 - 463 (2020/02/15)
Practical chiroptical sensing with a small group of commercially available aromatic aldehydes is demonstrated. Schiff base formation between the electron-deficient 2,4-dinitrobenzaldehyde probe and either primary amines, diamines, or amino alcohols proceeds smoothly in chloroform at room temperature and is completed in the presence of molecular sieves within 2.5 hours. The substrate binding coincides with a distinct circular dichroism signal induction at approximately 330 nm, which can be correlated to the absolute configuration and enantiomeric composition of the analyte. The usefulness of this sensing method is highlighted with the successful sensing of 18 aliphatic and aromatic amines and amino alcohols and five examples showing quantitative %ee determination with good accuracy.
A Resin-Bound Peptoid as a Recyclable Heterogeneous Catalyst for Oxidation Reactions
Stamatin, Yekaterina,Maayan, Galia
, p. 3147 - 3152 (2020/02/04)
Reusable solid-grafted catalysts have environmental and economical advantages over soluble catalysts. Numerous catalysts, including peptides, were immobilized on solid supports to enable their recyclability. Nevertheless, the few catalytic peptoids – N-substituted glycine oligomers – reported to date were only used off-resin. The soluble peptoids BT and DI, a trimer and dimer having two catalytic side-chains, were developed as bio-inspired oxidation catalysts. BT has an additional structure-directing group, which enables intramolecular cooperativity between the two catalytic groups (“intra-peptoid” mode). Thus, it catalyzes the oxidation of primary alcohols with much higher efficiency than DI. Herein, we present resin-bound BT and DI (TG-BT and TG-DI) as the first insoluble and recyclable catalytic peptoids. We discovered that though TG-BT also operates through the intra-peptoid cooperativity mode, it is less efficient than BT, even after several cycles. On the other hand, TG-DI is far more active than DI and can be recycled several times to enable a much higher turn-over-number. Our studies revealed that TG-DI operates through an intra-resin cooperativity mode, and this enables its high activity compared with DI, BT and TG-BT.
Iridium complexes with a new type of N^N′-donor anionic ligand catalyze the N-benzylation of amines via borrowing hydrogen
Ruiz-Casta?eda, Margarita,Rodríguez, Ana M.,Aboo, Ahmed H.,Manzano, Blanca R.,Espino, Gustavo,Xiao, Jianliang,Jalón, Félix A.
, (2020/10/14)
The development of efficient and eco-friendly methods for the synthesis of elaborate amines is highly desired as they are valuable chemicals. The catalytic alkylation of amines using alcohols as alkylating agents, through the so-called borrowing hydrogen process, satisfies several of the principles of green chemistry. In this paper, four neutral half-sandwich complexes of Ru(II), Rh(III), and Ir(III) have been synthesized and tested as catalysts in the N-benzylation of amines with benzyl alcohol. The new derivatives contain a N^N′ anionic ligand derived from 5-(pyridin-2-ylmethylene)hydantoin (Hpyhy) that has never been tested in metal complexes with catalytic applications. In particular, the Ir derivatives, [(Cp*)IrX(pyhy)] (X = Cl or H), exhibit high activity along with good selectivity in the process. Indeed, the scope of the optimized protocol has been proved in the benzylation of several primary and secondary amines. The selectivity towards monoalkylated or dialkylated amines has been tuned by adjusting the amine:alcohol ratio and the reaction time. Experimental results support a mechanism consisting of three consecutive steps, two of which are Ir catalyzed, and a favorable condensation step without the assistance of the catalyst. Moreover, an unproductive competitive pathway can operate when the reaction is performed in open-air vessels, due to the irreversible release of H2. This route is hampered when the reaction is carried out in close vessels, likely because the release of H2 is reversed through metal-based heterolytic cleavage. From our viewpoint, these results show the potential of the new catalysts in a very attractive and promising methodology for the synthesis of amines.
