65472-88-0Relevant academic research and scientific papers
THE BORONIC ACID MANNICH REACTION: A NEW METHOD FOR THE SYNTHESIS OF GEOMETRICALLY PURE ALLYLAMINES
Petasis, Nicos A.,Akritopoulou, Irini
, p. 583 - 586 (1993)
Reaction of vinyl boronic acids with the adducts of secondary amines and paraformaldehyde gives tertiary allylamines with the same geometry.This simple and practical method was used for the synthesis of geometrically pure naftifine, a potent antifungal agent.
Preparation method for synthesizing amine compound through co-catalysis and hydrosilylation of amide by iridium and boron reagents
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Paragraph 0035-0038, (2022/04/03)
The invention relates to a preparation method for synthesizing amine compounds from amide through co-catalysis and hydrosilylation of iridium and boron reagents, which comprises the following steps: reacting amide and silane in an organic solvent under the catalysis of an iridium complex and a boron reagent, and then concentrating and purifying to obtain amine, the molar ratio of the amide to the iridium complex to the boron reagent to the silane is 1: (0.0001-0.001): (0.01-0.05): (2-4); according to the invention, the amide which is stable and easy to obtain is used as a raw material, the iridium complex with very low catalyst loading capacity and the boron reagent are co-catalyzed for hydrosilylation, and the amine compound is efficiently synthesized. The method has the advantages of simple operation and separation of each step, fast reaction rate, mild reaction conditions, cheap and easily available commercial reagents, high yield and good functional group tolerance.
Amine compound as well as preparation method and application thereof
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Paragraph 0077; 0083-0086, (2021/08/21)
The invention discloses an amine compound containing allyl or benzyl as well as a preparation method and application of the amine compound. The preparation method comprises the steps of sequentially adding a raw material 1, amine, a catalyst and an additive into a reaction solvent, and stirring and reacting for 12-24 hours in an air atmosphere at the temperature of 50-120 DEG C to obtain a reaction solution, wherein the raw material 1 is allyl alcohol or benzyl alcohol, and the molar volume ratio of the raw material 1 to the amine to the catalyst to the additive to the reaction solvent is (0.2 to 8) mmol: (0.4 to 12) mmol: (0.01 to 0.4) mmol: (0.01 to 0.4) mmol: (2 to 40) mL; and removing the reaction solvent of the reaction solution, and then carrying out purification through thin layer chromatography/column chromatography, wherein a developing solvent system is petroleum ether/ethyl acetate, and the amine compound containing allyl or benzyl is obtained. The amine compound can be applied to preparation of framework of biological and pharmaceutical active molecules. The preparation method disclosed by the invention is wide in applicable substrate range, convenient to operate, green and environment-friendly.
Oxidative Rearrangement of MIDA (N-Methyliminodiacetic Acid) Boronates: Mechanistic Insights and Synthetic Applications
Kaldas, Sherif J.,Tien, Chieh-Hung,Gomes, Gabriel Dos Passos,Meyer, Stephanie,Sirvinskas, Martynas,Foy, Hayden,Dudding, Travis,Yudin, Andrei K.
supporting information, p. 324 - 328 (2021/01/26)
Herein we report that coordinative hemilability allows the MIDA (N-methyliminodiacetic acid) nitrogen to behave as a nucleophile and intramolecularly intercept palladium π-allyl intermediates. A mechanistic investigation indicates that this rearrangement proceeds through an SN2-like displacement at tetrasubstituted boron to furnish novel DABN boronates. Oxidative addition into the N-C bond of the DABN scaffold furnishes borylated π-allyl intermediates that can then be trapped with a variety of nucleophiles, including in a three-component coupling.
N -Butylpyrrolidone (NBP) as a non-toxic substitute for NMP in iron-catalyzed C(sp2)-C(sp3) cross-coupling of aryl chlorides
Bisz, Elwira,Koston, Martina,Szostak, Michal
supporting information, p. 7515 - 7521 (2021/10/12)
Although iron catalyzed cross-coupling reactions show extraordinary promise in reducing the environmental impact of more toxic and scarce transition metals, one of the main challenges is the use of reprotoxic NMP (NMP = N-methylpyrrolidone) as the key ligand to iron in the most successful protocols in this reactivity platform. Herein, we report that non-toxic and sustainable N-butylpyrrolidone (NBP) serves as a highly effective substitute for NMP in iron-catalyzed C(sp2)-C(sp3) cross-coupling of aryl chlorides with alkyl Grignard reagents. This challenging alkylation proceeds with organometallics bearing β-hydrogens with efficiency superseding or matching that of NMP with ample scope and broad functional group tolerance. Appealing applications are demonstrated in the cross-coupling in the presence of sensitive functional groups and the synthesis of several pharmaceutical intermediates, including a dual NK1/serotonin inhibitor, a fibrinolysis inhibitor and an antifungal agent. Considering that the iron/NMP system has emerged as one of the most powerful iron cross-coupling technologies available in both academic and industrial research, we anticipate that this method will be of broad interest.
Direct N-Alkylation/Fluoroalkylation of Amines Using Carboxylic Acids via Transition-Metal-Free Catalysis
Lu, Chunlei,Qiu, Zetian,Xuan, Maojie,Huang, Yan,Lou, Yongjia,Zhu, Yiling,Shen, Hao,Lin, Bo-Lin
supporting information, p. 4151 - 4158 (2020/08/21)
A scalable protocol of direct N-mono/di-alkyl/fluoroalkylation of primary/secondary amines has been constructed with various carboxylic acids as coupling agents under the catalysis of a simple air-tolerant inorganic salt, K3PO4. Advantageous features include 100 examples, 10 drugs and drug-like amines, fluorinated complex tertiary amines, gram-scale synthesis and isotope-labelling amine, thus demonstrating the potential applicability in industry of this methodology. The involvement of relatively less reactive silicon-hydride compared with the traditional reactive metal-hydride or boron-hydride species required to reduce the amide intermediates presumably contributes to the remarkable functional group compatibility. (Figure presented.).
A General Acid-Mediated Hydroaminomethylation of Unactivated Alkenes and Alkynes
Kaiser, Daniel,Tona, Veronica,Gon?alves, Carlos R.,Shaaban, Saad,Oppedisano, Alberto,Maulide, Nuno
supporting information, p. 14639 - 14643 (2019/09/17)
In comparison to the extensively studied metal-catalyzed hydroamination reaction, hydroaminomethylation has received significantly less attention despite its considerable potential to streamline amine synthesis. State-of-the-art protocols for hydroaminomethylation of alkenes rely largely on transition-metal catalysis, enabling this transformation only under highly designed and controlled conditions. Here we report a broadly applicable, acid-mediated approach to the hydroaminomethylation of unactivated alkenes and alkynes. This methodology employs cheap, readily available, and bench-stable reactants and affords the desired amines with excellent functional group tolerance and impeccable regioselectivity. The broad scope of this transformation, as well as mechanistic investigations and in situ domino functionalization reactions are reported.
Metal-Organic Capsules with NADH Mimics as Switchable Selectivity Regulators for Photocatalytic Transfer Hydrogenation
Wei, Jianwei,Zhao, Liang,He, Cheng,Zheng, Sijia,Reek, Joost N. H.,Duan, Chunying
, p. 12707 - 12716 (2019/09/04)
Switchable selective hydrogenation among the groups in multifunctional compounds is challenging because selective hydrogenation is of great interest in the synthesis of fine chemicals and pharmaceuticals as a result of the importance of key intermediates. Herein, we report a new approach to highly selectively (>99%) reducing C=X (X = O, N) over the thermodynamically more favorable nitro groups locating the substrate in a metal-organic capsule containing NADH active sites. Within the capsule, the NADH active sites reduce the double bonds via a typical 2e- hydride transfer hydrogenation, and the formed excited-state NAD+ mimics oxidize the reductant via two consecutive 1e- processes to regenerate the NADH active sites under illumination. Outside the capsule, nitro groups are highly selectively reduced through a typical 1e- hydrogenation. By combining photoinduced 1e- transfer regeneration outside the cage, both 1e- and 2e- hydrogenation can be switched controllably by varying the concentrations of the substrates and the redox potential of electron donors. This promising alternative approach, which could proceed under mild reaction conditions and use easy-to-handle hydrogen donors with enhanced high selectivity toward different groups, is based on the localization and differentiation of the 2e- and 1e- hydrogenation pathways inside and outside the capsules, provides a deep comprehension of photocatalytic microscopic reaction processes, and will allow the design and optimization of catalysts. We demonstrate the advantage of this method over typical hydrogenation that involves specific activation via well-modified catalytic sites and present results on the high, well-controlled, and switchable selectivity for the hydrogenation of a variety of substituted and bifunctional aldehydes, ketones, and imines.
Design of two alternative routes for the synthesis of naftifine and analogues as potential antifungal agents
Abonia, Rodrigo,Garay, Alexander,Castillo, Juan C.,Insuasty, Braulio,Quiroga, Jairo,Nogueras, Manuel,Cobo, Justo,Butassi, Estefanía,Zacchino, Susana
, (2018/03/09)
Two practical and efficient approaches have been implemented as alternative procedures for the synthesis of naftifine and novel diversely substituted analogues 16 and 20 in good to excellent yields, mediated by Mannich-type reactions as the key step of the processes. In these approaches, theγ-aminoalcohols 15 and 19 were obtained as the key intermediates and their subsequent dehydration catalyzed either by Br?nsted acids like H2SO4 and HCl or Lewis acid like AlCl3, respectively, led to naftifine, along with the target allylamines 16 and 20. The antifungal assay results showed that intermediates 18 (bearing both a β-aminoketo- and N-methyl functionalities in their structures) and products 20 were the most active. Particularly, structures 18b, 18c, and the allylamine 20c showed the lowest MIC values, in the 0.5-7.8 μg/mL range, against the dermatophytes Trichophyton rubrum and Trichophyton mentagrophytes. Interesting enough, compound 18b bearing a 4-Br as the substituent of the phenyl ring, also displayed high activity against Candida albicans and Cryptococcus neoformans with MIC80 = 7.8 μg/mL, being fungicide rather than fungistatic with a relevant MFC value = 15.6 μg/mL against C. neoformans.
Methylation method of amines
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Paragraph 0091; 0092; 0093; 0094; 0095; 0096, (2017/12/04)
The invention provides a methylation method of amines. The method is characterized by comprising the steps that under the protection of nitrogen or inert gas, organic amines, a reductive agent polymethyl hydrogen siloxane or diphenyl silane, a catalyst potassium phosphate and an additive 18-crown-6 are added into a reaction container, and an reaction is made with carbon dioxide as a C1 source to obtain methylated products of amines. According to the method, potassium phosphate serves as the catalyst, the carbon dioxide serves as the C1 source, polymethyl hydrogen siloxane or diphenyl silane serves as the reductive agent, and 18-crown-6 serves as the additive. Various kinds of amines are converted into the corresponding methylated products in an acetonitrile solvent or without solvents. Two waste materials including the carbon dioxide and polymethyl hydrogen siloxane (PMHS) serve as the C1 source and the reductive agent in the method respectively, phosphate serves as the catalyst, the cost is low, and the conversion efficiency is high. Thus, the method makes an important contribution to the development of green chemistry.
