多相双金属Pt-Sn/γ-Al_2O_3催化的胺N-烷基化反应合成仲胺和叔胺

基于借氢策略、醇为烷基化试剂的胺的N-烷基化反应是合成胺类化合物的绿色途径.在无外加氢源条件下,多相双金属Pt-Sn/γ-Al2O3催化剂可高效催化醇为烷基化试剂的伯(仲)胺的N-烷基化反应合成仲(叔)胺,反应副产物为水与极少量亚胺.催化体系的底物适应性好,目标产物收率高;催化剂可以循环使用,具有潜在的工业化应用前景.     

甲醇为氢源的连续化催化转移加氢合成芳胺

开发了一种温和高效的以甲醇为氢源,以Ru-Fe双金属催化剂催化的硝基芳烃连续化转移加氢方法。采用浸渍法制备Ru-Fe双金属催化剂,通过电感耦合等离子体-质谱(ICP-MS)、透射电子显微镜(TEM)、X射线衍射(XRD）、氢气程序升温还原(H₂-TPR)对催化剂进行表征。结果表明催化剂具有较小的粒径和较好的分散性。在Ru-Fe双金属催化剂上,成功实现了硝基芳烃与甲醇在无外加氢源条件下的连续化转移加氢合成芳胺。通过对反应条件的调控,成功得到了一系列产率较高的胺类化合物。特别地,该方法对不饱和基团(醛基、羰基或炔基)取代的硝基芳烃的加氢表现出优异的选择性和转化率。     

烯烃的氢甲酰化串联反应研究

氢甲酰化串联反应是在氢甲酰化反应的基础上,与一个或多个不同类型的反应“一锅法”实现醛类化合物的后续定向转化,得到新的有机分子的合成方法。该反应的产物在日化工业、农业、医药中间体的生产中具有十分重要的用途。本文首先简述了近年来烯烃氢甲酰化串联反应制备高附加值化学品的重要性,随后重点介绍了几种常见的烯烃氢甲酰化串联反应:“异构化-氢甲酰化”串联反应、“氢甲酰化-缩醛化”串联反应、“氢甲酰化-氢化”串联反应和“氢甲酰化-(还原)胺化”串联反应等,以及其在设计新型(多功能)催化剂体系和高效合成目标产物方面的研究进展,最后总结了烯烃氢甲酰化串联反应存在的问题以及对未来发展趋势进行了展望。     

钯催化卤代芳烃的胺化反应研究

钯催化卤代芳烃胺化是形成Car-N的重要方法.配体的发展扩展了底物的适用范围, 提高了反应的选择性,实现了廉价易得的氯代芳烃的胺化,弱碱的使用提高了官能团的兼 容性,因此Pd催化芳胺化广泛应用于合成芳胺类化合物.本文以卤代芳烃为线索,对钯催化偶联胺化反应的研究进展进行了综述和展望.     

钯催化卤代芳烃的胺化反应的研究进展

钯催化卤代芳烃的胺化是合成芳胺化合物的重要方法,综述了近年来钯催化卤代芳烃与胺等不同含氮化合物的胺化反应研究进展,重点讨论了钯催化剂配体的结构、反应物比例、溶剂及温度等因素对反应的影响.     

钯催化芳香硝基化合物与烯烃的选择性还原羰化酰胺化反应

与芳香胺相比,芳香硝基化合物具有廉价易得、官能团兼容性好等优点,作为氮源在下游含氮化学品合成中具有广泛的应用.目前烯烃羰化酰胺化反应绝大多数以胺类化合物为氮源,其中直链和支链酰胺产物的选择性主要是通过具有特定电子和位阻特性的配体调控实现.已报道的芳香硝基化合物的还原酰胺化反应研究中,需要外加还原剂或者利用金属羰基化合物Mo(CO)6释放的CO为羰基源和还原剂.本文发展了一种毋须外加还原剂的钯催化芳香硝基化合物与烯烃的还原羰化酰胺化反应新方法.研究发现,钯金属催化剂(特别是离子型)的抗衡阴离子是还原羰化酰胺化反应中化学选择性和羰化区域选择性的关键因素.抗衡阴离子为氯离子、硼酸为助剂时,最优钯前驱物K2PdCl4的产物主要为支链酰胺,此时不同的膦配体并不能调控其区域选择性,这与胺的烯烃酰胺化反应可以通过配体调控羰化的区域选择性表现出明显的不同.含氮中间体原位捕捉、硝基化合物还原下游可能中间体对照实验等研究表明,芳香硝基化合物在以一氧化碳为还原剂的催化还原体系下被完全脱氧还原为氮烯(Ar-N:),再经过烯酰胺中间体进一步烯键还原得到相应的支链酰胺;当离子型钯前驱物的抗衡阴离子配位性较弱时,最优钯前驱物为Pd(CH3CN)4(OTf)2时,以直链酰胺为主要产物,此时不同的膦配体可以调控酰胺化的区域选择性.同样的机理研究表明,在该催化剂体系下芳香硝基化合物首先被还原为芳基胺,然后再发生与现有报道类似的胺类化合物的烯烃羰化酰胺化反应.这两个催化反应体系都表现出了较好的底物适用性,并且可以高效地应用于除草剂(敌稗)的一步合成.本文为以硝基化合物为起始氮源,通过催化控制生成特定含氮中间体,从而可控合成不同的含氮化学品提供了一条新思路.     

甲醇为氢源的连续化催化转移加氢合成芳胺

开发了一种温和高效的以甲醇为氢源，以Ru-Fe双金属为催化剂的硝基芳烃连续化转移加氢方法。采用浸渍法制备Ru-Fe双金属催化剂，通过电感耦合等离子体-质谱(ICP-MS)、透射电子显微镜(TEM)、X射线衍射(XRD）、氢气程序升温还原(H₂-TPR)对催化剂进行表征。结果表明催化剂具有较小的粒径和较好的分散性。在Ru-Fe双金属催化剂上，成功实现了硝基芳烃与甲醇在无外加氢源条件下的连续化转移加氢合成芳胺。通过对反应条件的调控，成功得到了一系列产率较高的胺类化合物。特别地，该方法对不饱和基团(醛基、羰基或炔基)取代的硝基芳烃的加氢表现出优异的选择性和转化率。     

氮掺杂碳材料负载Pd纳米结构催化剂催化硝基芳烃与苄醇借氢还原偶联制备亚胺

亚胺化合物作为一类重要的有机合成中间体,在医药、染料以及精细化学品制备方面具有重要的应用价值.使用竹笋为生物质原料制备一种氮掺杂碳材料负载的Pd纳米结构催化剂,以醇为氢源和反应物,通过借氢还原策略实现硝基芳烃原位还原并偶联反应高效制备亚胺化合物.该催化剂相对于其他商业化的催化剂和载体具有明显的性能优势,催化体系具有良好...     

Co@CoO催化剂表面类氢负物种NH2δ-驱动下的还原胺化反应(英文)

胺类化合物作为一类重要的精细化学品,广泛应用于合成染料、表面活性剂、聚合物、药品和农用化学品.催化还原胺化是合成胺类化合物的重要手段.在还原胺化反应中,水是唯一的副产物,且反应条件温和,符合绿色化学原则,因此受到了广泛关注.在过去的几十年里,生物质衍生的羰基化合物(糠醛、环戊酮、5-羟甲基糠醛等)的催化还原胺化得到了特别关注,为利用可再生资源可持续地生产胺类提供了可能性.通常,金属(Ru, Ir, Pt, Rh, Co, Ni等)被认为是还原胺化的活性中心,相关研究快速发展,但大部分研究都围绕着金属负载型催化剂展开,对于以金属氧化物为活性中心鲜有研究.另外,还原胺化过程研究表明,席夫碱在反应开始阶段迅速生成,然后通过氨解产生相应的伯胺;但席夫碱氨解为伯胺的过程速率较慢,是该反应的决速步骤,因此设计高效催化剂加快席夫碱的氨解是还原胺化过程中的重要科学问题.受孤立的路易斯酸碱对可以催化氢气异裂过程的启发,本文利用具有核壳结构的Co@Co O为催化剂,发现表面具有氧空位的CoO具有独特的解离NH₃生成类氢负物种(NH₂^δ-)的...     

金属-有机骨架衍生的Co单原子高效催化硝基芳烃氢化还原

芳香胺及其衍生物是药物、染料、除草剂等的重要原料或关键中间体,开发高效、低成本、高选择性的硝基芳烃还原催化剂具有重要的现实意义.以常见的沸石类咪唑骨架材料为模板,原位热解制备了一种Co单原子催化剂(Co-N-C),并以乙醇作溶剂,水合肼作氢源,实现了多种硝基芳烃的高效氢化还原.该Co-N-C材料制备简单,催化活性优异,所催化的硝基芳烃还原体系反应条件温和,官能团兼容性优异.天然产物应用实验、克级扩大实验、循环实验和抗浸出实验证实了Co-N-C的高效性和还原体系的实用性.另外,通过反应过程检测,提出了Co-N-C催化硝基芳烃直接还原和缩合还原的两种反应机理.     

General and selective synthesis of primary amines using Ni-based homogeneous catalysts

The development of base metal catalysts for industrially relevant amination and hydrogenation reactions by applying abundant and atom economical reagents continues to be important for the cost-effective and sustainable synthesis of amines which represent highly essential chemicals. In particular, the synthesis of primary amines is of central importance because these compounds serve as key precursors and central intermediates to produce value-added fine and bulk chemicals as well as pharmaceuticals, agrochemicals and materials. Here we report a Ni-triphos complex as the first Ni-based homogeneous catalyst for both reductive amination of carbonyl compounds with ammonia and hydrogenation of nitroarenes to prepare all kinds of primary amines. Remarkably, this Ni-complex enabled the synthesis of functionalized and structurally diverse benzylic, heterocyclic and aliphatic linear and branched primary amines as well as aromatic primary amines starting from inexpensive and easily accessible carbonyl compounds (aldehydes and ketones) and nitroarenes using ammonia and molecular hydrogen. This Ni-catalyzed reductive amination methodology has been applied for the amination of more complex pharmaceuticals and steroid derivatives. Detailed DFT computations have been performed for the Ni-triphos based reductive amination reaction, and they revealed that the overall reaction has an inner-sphere mechanism with H₂ metathesis as the rate-determining step.

A Ni-triphos based homogeneous catalyst enabled the synthesis of all kinds of primary amines by reductive amination of carbonyl compounds with ammonia and hydrogenation of nitroarenes.     

High performance of nitrogen-doped carbon-supported cobalt catalyst for the mild and selective synthesis of primary amines

A nitrogen-doped carbon-supported Co catalyst (Co/N-C-800) was discovered to be highly active for the reductive amination of carbonyl compounds with NH₃ and the hydrogenation of nitriles into primary amines using H₂ as the hydrogen source. Structurally diverse carbonyl compounds were selectively transformed into primary amines with good to excellent yields (82.8–99.6%) under mild conditions. The Co/N-C-800 catalyst showed comparable or better catalytic performance than the reported noble metal catalysts. The Co/N-C-800 catalyst also showed high activity for the hydrogenation of nitriles, affording the corresponding primary amines with high yields (81.7–99.0%). An overall reaction mechanism is proposed for the reductive amination of benzaldehyde and the hydrogenation of benzonitrile, which involves the same intermediates of phenylmethanimine and N-benzylidenebenzylamine.     

Fast Reductive Amination by Transfer Hydrogenation “on Water”

Reductive amination of various ketones and aldehydes by transfer hydrogenation under aqueous conditions has been developed, by using cyclometallated iridium complexes as catalysts and formate as hydrogen source. The pH value of the solution is shown to be critical for a high catalytic chemoselectivity and activity, with the best pH value being 4.8. In comparison with that in organic solvents, the reductive amination in an aqueous phase is faster, and the molar ratio of the substrate to the catalyst (S/C) can be set as high as 1×10⁵, the highest S/C value ever reported in reductive amination reactions. The catalyst is easy to access and the reaction is operationally simple, allowing a wide range of ketones and aldehydes to react with various amines in high yields. The protocol provides a practical and environmental friendly new method for the synthesis of amine compounds.     

Rhodium-terpyridine Catalyzed Transfer Hydrogenation of Aromatic Nitro Compounds in Water

A rhodium terpyridine complex catalyzed transfer hydrogenation of nitroarenes to anilines with i-PrOH as hydrogen source and water as solvent has been developed. The catalytic system can work at a substrate/catalyst (S/C) ratio of 2000, with a turnover frequency (TOF) up to 3360 h⁻¹, which represents one of the most active catalytic transfer hydrogenation systems for nitroarene reduction. The catalytic system is operationally simple and the protocol could be scaled up to 20 gram scale. The water-soluble catalyst bearing a carboxyl group could be recycled 15 times without significant loss of activity.     

Reductive Amination without an External Hydrogen Source

A method of reductive amination without an external hydrogen source is reported. Carbon monoxide is used as the reductant. The reaction proceeds efficiently for a variety of carbonyl compounds and amines at low catalyst loadings and is mechanistically interesting as it does not seem to involve molecular hydrogen.     

Earth-abundant Metal-catalyzed Reductive Amination: Recent Advances and Prospect for Future Catalysis

Nitrogen-containing compounds, as an important class of chemicals, have been used widely in pharmaceuticals, materials synthesis. Transition metal-catalyzed reductive amination of an aldehyde or a ketone with ammonia or an amine has been proved to be an efficient and practical method for the preparation of nitrogen-containing compounds in academia and industry for a century. Given the above, several effective methods using transition metals have been developed in recent years. Noble transition metals like Pd, Pt, and Au-based catalysts have been predominately used in reductive amination. Because of their high prices, strict official regulations of residues in pharmaceuticals, and deleterious effects on the biological system, their industrial applications are severely hampered. With the increasing sustainable and environmental problems, the Earth-abundant transition metals including Ti, Fe, Co, Ni, and Zr have also been investigated for the reductive amination reaction and showed great potential to the advancement of sustainable and cost-effective reductive amination processes. This critical review will mainly summarize the work using Earth-abundant metals. The effects of different transition metals used in catalytic reduction amination were discussed and compared, and some suggestions were given. The last section highlights the catalytic activities of bi- and tri-metallic catalysts. Indeed, this latter family is very promising and simultaneously benefits from increased stability, and selectivity, compared to monometallic NPs, due to synergistic substrate activation. Few comprehensive reviews focusing on Earth-abundant transition metals catalyst has been published since 1948, although several authors reported some summaries dealing with one or the other part of this aspect. It is hoped that this critical review will inspire researchers to develop new efficient and selective earth-abundant metal catalysts for highly, environmentally sustainable reductive amination methods, as well as improve the pharmaceutical industry and related chemical synthesis company traditional method with the utilization of the green method widely.     

Regio- and chemoselective catalytic transfer hydrogenation of aromatic nitro and carbonyl as well as reductive cleavage of azo compounds over novel mesoporous NiMCM-41 molecular sieves

[reaction: see text] [corrected] Regio- and chemoselective reduction of nitroarenes and carbonyl compounds and reductive cleavage of azo compounds, including bulkier molecules, was achieved by the catalytic transfer hydrogenation method (CTH) using a novel nickel-containing mesoporous silicate (NiMCM-41) molecular sieve catalyst. In addition, the catalyst was also found to behave as a truly heterogeneous catalyst as the yield was practically unaffected.     

Colloid and nanodimensional catalysts in organic synthesis: VIII. Hydrogenation of C=N bond with hydrogen in the presence of colloid nickel

Hydrogenation of azomethines with hydrogen at atmospheric pressure using nickel nanoparticles as catalyst was carried out. Reaction may be used for the preparation of secondary amines under mild conditions on an available catalyst. Continuation of studies will lead to development of a convenient method for the reductive amination of carbonyl compounds.     

Ruthenium-catalyzed tertiary amine formation from nitroarenes and alcohols

A highly selective ruthenium-catalyzed C-N bond formation was developed by using the hydrogen-borrowing strategy. Various tertiary amines were obtained efficiently from nitroarenes and primary alcohols. The reaction tolerates a wide range of functionalities. A tentative mechanism was proposed for this direct amination reaction of alcohols with nitroarenes.     

Highly chemoselective reductive amination by one pot reaction of aldehydes, amines and Dihydropyridine Catalyzed by TMSCl

More efficient, cost effective and metal free DHP/TMSCl system for one pot reductive amination of aldehydes was developed. The method allows the efficient one pot synthesis of structurally diverse amines with Hantzsch ester as the hydrogen source in the presence of trimethylsilyl chloride as a catalyst in high to quantitative yields under mild conditions.