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1.
Primary Amines by Transfer Hydrogenative Reductive Amination of Ketones by Using Cyclometalated IrIII Catalysts
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Dinesh Talwar Noemí Poyatos Salguero Dr. Craig M. Robertson Prof. Jianliang Xiao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(1):245-252
Cyclometalated iridium complexes are found to be versatile catalysts for the direct reductive amination (DRA) of carbonyls to give primary amines under transfer‐hydrogenation conditions with ammonium formate as both the nitrogen and hydrogen source. These complexes are easy to synthesise and their ligands can be easily tuned. The activity and chemoselectivity of the catalyst towards primary amines is excellent, with a substrate to catalyst ratio (S/C) of 1000 being feasible. Both aromatic and aliphatic primary amines were obtained in high yields. Moreover, a first example of homogeneously catalysed transfer‐hydrogenative DRA has been realised for β‐keto ethers, leading to the corresponding β‐amino ethers. In addition, non‐natural α‐amino acids could also be obtained in excellent yields with this method. 相似文献
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《中国化学》2017,35(9):1371-1377
Heterogeneous iridium catalysts were prepared and applied for the reductive amination of aldehydes and ketones with nitroaromatics and amines using H2 . The iridium catalysts were prepared by pyrolysis of ionic liquid 1‐methyl‐3‐cyanomethylimidazoulium chloride ([MCNI ]Cl) with iridium chloride (IrCl3 ) in activated carbons. Iridium particles were well dispersed and stable in the N‐doped carbon materials from [MCNI ]Cl with activated carbon. The Ir@NC (600‐2h) catalyst was found to be highly active and selective for the reductive amination of aldehydes and ketones using H2 and a variety of nitrobenzenes and amines were selectively converted into the corresponding secondary and tertiary amines. The Ir@NC (600‐2h) catalyst can be reusable several times without evident deactivation. 相似文献
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Mohamed Ali Ayedi Yves Le Bigot Souhir Abid Rachid El Gharbi Michel Delmas 《合成通讯》2013,43(16):2127-2133
We report here a novel, one-pot, two-step reductive amination of aldehydes for the atom-economical synthesis of primary amines. The amination step has been carried out with hydroxylammonium chloride and does not require the use of a base. In the subsequent reduction step, a metal zinc/hydrochloride acid system has been used. This method is applicable to both aliphatic and aromatic aldehydes. The operational simplicity, the short reaction times, and the mild reaction conditions add to the value of this method as a practical alternative to the reductive amination of aldehydes. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file. 相似文献
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Dr. Matthieu Jouffroy Thi-Mo Nguyen Marie Cordier Marielle Blot Dr. Thierry Roisnel Dr. Rafael Gramage-Doria 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(36):e202201078
Direct reductive amination (DRA) is a ubiquitous reaction in organic chemistry. This transformation between a carbonyl group and an amine is most often achieved by using a super stoichiometric amount of hazardous hydride reagents, thus being incompatible with many sensitive functional groups. DRA could also be achieved by means of chemo- or biocatalysis, thereby attracting the interest of industry as well as academic laboratories due to the virtually perfect atom economy. Although DRAs are well-established for substrate pairs such as aldehydes with either 1° or 2° amines as well as ketones with 1° amines, the current methodologies are limited in the case of ketones with 2° amines. Herein, we present a general DRA protocol that overcomes this major limitation by means of iridium catalysis. The applicability of the methodology is demonstrated by accessing an unprecedented range of biologically relevant tertiary amines starting from both aliphatic ketones and aliphatic amines. The choice of a disphosphane ligand (Josiphos A or Xantphos) is essential for the success of the transformation. 相似文献
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Iuliia Polishchuk Dr. Jan Sklyaruk Dr. Yury Lebedev Prof. Dr. Magnus Rueping 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(19):5919-5922
Half-sandwich iridium complexes bearing bidentate urea-phosphorus ligands were found to catalyze the direct reductive amination of aromatic and aliphatic ketones under mild conditions at 0.5 mol % loading with high selectivity towards primary amines. One of the complexes was found to be active in both the Leuckart–Wallach (NH4CO2H) type reaction as well as in the hydrogenative (H2/NH4AcO) reductive amination. The protocol with ammonium formate does not require an inert atmosphere, dry solvents, as well as additives and in contrast to previous reports takes place in hexafluoroisopropanol (HFIP) instead of methanol. Applying NH4CO2D or D2 resulted in a high degree of deuterium incorporation into the primary amine α-position. 相似文献
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Le' an Hu Yao Zhang Qing‐Wen Zhang Qin Yin Xumu Zhang 《Angewandte Chemie (International ed. in English)》2020,59(13):5321-5325
A Ru‐catalyzed direct asymmetric reductive amination of ortho‐OH‐substituted diaryl and sterically hindered ketones with ammonium salts is reported. This method represents a straightforward route toward the synthesis of synthetically useful chiral primary diarylmethylamines and sterically hindered benzylamines (up to 97 % yield, 93–>99 % ee). Elaborations of the chiral amine products into bioactive compounds and a chiral ligand were demonstrated through manipulation of the removable and convertible ‐OH group. 相似文献
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By applying a simple Pd/NiO catalyst, the reductive amination of amines and aldehydes can progress efficiently under mild reaction conditions, and 24 substituted amines with different structures were synthesized with up to 98% isolated yields. 相似文献
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微波干法催化醛酮与胺的缩合反应 总被引:2,自引:1,他引:2
利用微波辐射和固体中性Al2 O3 载体催化醛酮与胺的缩合反应的方法合成了十六种亚胺 ,研究了微波功率、作用时间、产物提取方式等因素对反应的影响 ;与无微波作用的一般合成方法相比 ,该法明显地提高反应速度及产率 ;文中用低极性熔点递变物质灌装毛细管的方法观测微波作用下反应温度 ,探讨微波作用化学反应的机理 ,其机理除与微波加热作用有关外还与分子间氢键及分子的缔合性有关。 相似文献
11.
Sofiya A. Runikhina Dr. Oleg I. Afanasyev Klim Biriukov Prof. Dr. Dmitry S. Perekalin Dr. Martin Klussmann Dr. Denis Chusov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(71):16225-16229
Common and non-toxic aldehydes are proposed as reagents for alkylation of ketones instead of carcinogenic alkyl halides. The developed reductive alkylation reaction proceeds in the presence of the commercially available ruthenium catalyst [(cymene)RuCl2]2 (as low as 250 ppm) and carbon monoxide as the reducing agent. The reaction works well for a broad substrate scope, including aromatic and aliphatic aldehydes and ketones. It can be carried out without a solvent and often gives nearly quantitative yields of the products. This straightforward and cost-effective method is promising not only for laboratory application but also for industry, which produces carbon monoxide as a large-scale waste product. 相似文献
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K. Nagaiah V. Naveen Kumar R. Srinivasa Rao B. V. S. Reddy A. V. Narsaiah J. S. Yadav 《合成通讯》2013,43(22):3345-3352
The imines were generated in situ from carbonyl compounds and amines, which undergo smooth reduction with sodium borohydride in an ionic liquid/H2O solvent system. The reaction conditions were very mild and neutral to afford the corresponding highly functionalized amines in excellent yields. 相似文献
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Direct reductive amination of aldehydes and ketones were accomplished efficiently using high-capacity, ionene-based, polymer-supported borohydride reagent in isopropyl alcohol at reflux under neutral conditions. The reagent is easily prepared by mixing aqueous solution of 2,4-ionene bromide with an alkaline solution of sodium borohydride at room temperature. The generality of reaction was established using both aliphatic and aromatic aldehydes, ketones, and amines. 相似文献
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A one-pot tandem direct reductive amination of aldehydes with primary amines resulting in N-Boc secondary amines using a (Boc)(2)O/sodium triacetoxyborohydride (STAB) system is reported. The tandem procedure is efficient, selective, and versatile, giving excellent yields of N-Boc protected secondary amines even in those cases where the products are prone to intramolecular lactamization. 相似文献
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《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2017,129(11):3096-3100
Transformation of biomass into valuable nitrogen‐containing compounds is highly desired, yet limited success has been achieved. Here we report an efficient catalyst system, partially reduced Ru/ZrO2, which could catalyze the reductive amination of a variety of biomass‐derived aldehydes/ketones in aqueous ammonia. With this approach, a spectrum of renewable primary amines was produced in good to excellent yields. Moreover, we have demonstrated a two‐step approach for production of ethanolamine, a large‐market nitrogen‐containing chemical, from lignocellulose in an overall yield of 10 %. Extensive characterizations showed that Ru/ZrO2‐containing multivalence Ru association species worked as a bifunctional catalyst, with RuO2 as acidic promoter to facilitate the activation of carbonyl groups and Ru as active sites for the subsequent imine hydrogenation. 相似文献
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The broad applications of primary alkyl amines in various fields have spurred extensive interests in synthetic organic chemistry. Recently, the reductive amination of carboxylic acids has become an attractive and practical strategy for synthesizing primary alkyl amines, due to their wide availability and bench stability. However, the inherent stability and higher oxidation state of carboxylic acids render this new strategy with new challenges. This Concept provides a summary of the recent advancements in the reductive aminations of carboxylic acids, specifically focusing on the catalytic tactics, underlying mechanisms, and applications in the synthesis of valuable products. 相似文献
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Tingting Li Qian Zhou Fanjing Meng Wenhui Cui Qian Li Jiang Zhu Yang Cao 《European journal of organic chemistry》2023,26(37):e202300507
This review summarizes the recent progress of organocatalytic and biocatalytic asymmetric reductive amination (ARA), a challenging but important topic for drug discovery and the pharmaceutical industry. At present, ARA can be divided into three categories: metal catalysis, organic catalysis, and biocatalysis. In the past decade, transition metal-catalysed ARA has been well established. Organocatalytic ARA has emerged as a powerful alternative to metal-catalysed ARA, the hydrogen sources used in organocatalytic ARA are usually Hantzsch esters, benzothiazolines, boranes, and hydrosilanes, which require Lewis base or phosphoric acid catalysts to activate them to give secondary chiral amines. It is worth mentioning that biocatalytic ARA has made remarkable progress in the last decade, amino acid dehydrogenases, amine dehydrogenases, opine dehydrogenases and imine reductases have been successfully used in ARA. 相似文献
20.
Rajanarendar Eligeti Siva Rami Reddy Atthunuri Raju Samala Firoz Pasha Shaik Govardhan Reddy Kundur 《中国化学》2011,29(4):769-772
Reductive amination of aromatic aldehydes using NaBH4 and isoxazole amines is carried out in a Brønsted acidic ionic liquid 1‐methylimidazolium tetrafluoroborate [(HMIm)BF4]. The ionic liquid plays dual roles of solvent as well as catalyst for the efficient transformation of aromatic aldehydes to heterocyclic substituted amines in excellent yields without any undesired side product formation. The newly synthesized compounds ( 3 , 6 and 7 ) were characterized by IR, 1H NMR and mass spectral techniques. 相似文献