烷基化胺类化合物是一类重要的化工中间体，广泛应用于医药,农药及染料等的合成。胺类化合物通常由胺与卤代烃反应制得。这种方法需要消耗化学计量的碱性助 剂，产生大量无机废渣，造成严重的环境污染。醇替代卤代烃作为反应原料，水是唯一的副产物，能够减少污染物的生成。传统上胺与醇反应制备取代胺类化合物主 要使用贵金属钌和铱等均相催化体系。高效非贵金属体系和负载纳米贵金属催化剂体系的研究对于开发廉价且环境友好的取代胺类化合物的制备方法具有非常重要的 意义。近年来，我们对Cu(OAc)2，FeCl2等非贵金属催化体系、RuCl3催化体系以及Ag-Mo，Pd/Fe2O3，Au/Fe2O3等多相催 化体系的制备及其催化取代胺类化合物的清洁合成进行了系统的研究，针对磺酰胺、碳酰胺、胺类和硝基化合物与醇反应一步烷基化发展出了多个清洁、高效的催化 剂体系1-4，式一。

石峰,崔新江,张妍,等. 基于胺-醇烷基化制备取代胺类化合物的清洁催化体系研究[C]. 第二十八届中国化学会年会第1分会场摘要集.2012,186.

硝基苯类化合物的催化加氢是催化化学和化学化工领域的重要反应,如果能够实现对不同功能基团的选择性加氢和对不同结构硝基苯的选择加氢无疑将是非常有意义 的1,2。在这里,我们使用离子液体作为模板制备了一系列氧化硅负载炭改性的纳米钌催化剂。在催化剂制备中,离子液体是三氯化钌的溶剂,纳米钌改性的炭源 同时又是获得合适二氧化硅结构的模板剂(图一)。经过系列的TEM、XPS、XRD和BET等表征和性能研究，我们发现使用1-丁基-3-甲基咪唑四氟硼 酸盐离子液体时可以获得最佳的结构和性能(图二)。

崔新江,袁航空,石峰,等. 离子液体导向二氧化硅负载炭改性纳米钌催化剂的制备及其在催化硝基苯加氢反应中的择形性研究[C]. 第二十八届中国化学会年会第1分会场摘要集.2012,185.

CO₂/H₂ was successfully employed in alkylation reactions by performing CO₂ reduction and amine N-methylation in one-pot. In the presence of a simple CuAlO_x catalyst, N-methyl or N,N-dimethyl amines with different structures can be selectively synthesized with up to 96% yields by applying amine, nitrobenzene and nitrile as starting materials.

★★★☆☆ Cui XJ,Dai XC,Zhang Y,et al. Methylation Of Amines, Nitrobenzenes And Aromatic Nitriles With Carbon Dioxide And Molecular Hydrogen[J]. Chemical Science,2014,5:649-655.

A simple and efficient Pd/Al₂O₃-NR-RD catalyst was prepared by depositing palladium on a shape controllable Al₂O₃-NR support through a two-step process that involves hydrothermal synthesis of Al₂O₃-NR_s followed by reductive-deposition of palladium. This catalyst showed high activity in the catalytic formylation of amines by CO₂–H₂ under mild conditions with up to 96% yield.

★★★★☆ Cui XJ,Zhang Y,Deng YQ,et al. Amine Formylation Via Carbon Dioxide Recycling Catalyzed By A Simple And Efficient Heterogeneous Palladium Catalyst[J]. Chemical Communications,2013,50:189-191.

As the sustainable and promising hydrogen source, here, glycerol was directly used as the hydrogen source for the reductive amination of alcohol using nitrobenzene as the starting material. The amination of alcohols, especially aliphatic alcohols with different structures, was realized, and mono- or disubstituted amines were synthesized with excellent yields. The reaction mechanism was also explored.

KEYWORDS: amines, alcohols, N-alkylation, glycerol, renewable, catalysis

★★★☆☆ xinjiang Cui,Youquan Deng,Feng Shi. Reductive N‑alkylation Of Nitro Compounds To N‑alkyl And N,n‑dialkyl Amines With Glycerol As The Hydrogen Source[J]. Acs Catalysis,2013,3:808-811.

The N-alkylation of amines or ammonia with alcohols is a valuable route for the synthesis of N-alkyl amines. However, as a potentially clean and economic choice for N-alkyl amine synthesis, non-noble metal catalysts with high activity and good selectivity are rarely reported. Normally, they are severely limited due to low activity and poor generality. Herein, a simple NiCu-FeO_x catalyst was designed and prepared for the N-alkylation of ammonia or amines with alcohol or primary amines. N-alkyl amines with various structures were successfully synthesized in moderate to excellent yields in the absence of organic ligands and bases. Typically, primary amines could be efficiently transformed into secondary amines and N-heterocyclic compounds, and secondary amines could be N-alkylated to synthesize tertiary amines. Note that primary and secondary amines could be produced through a one-pot reaction of ammonia and alcohols. In addition to excellent catalytic performance, the catalyst itself possesses outstanding superiority, that is, it is air and moisture stable. Moreover, the magnetic property of this catalyst makes it easily separable from the reaction mixture and it could be recovered and reused for several runs without obvious deactivation.

Keywords: alcohols · amination ·ammonia · heterogeneous catalysis ·non-noble metals

★★★☆☆ Cui XJ,Dai XC,Deng YQ,et al. Development Of A General Non-noble Metal Catalyst For The Benign Amination Of Alcohols With Amines And Ammonia[J]. Chemistry A-europeann Journal,2013,19(11):3665-3675.

A Pd–Au/SiO2 catalyst was prepared for the oxidative imination of toluenes with up to 99% yields in the absence of dehydrating agents under mild conditions. Nanoparticles with a PdO layer and PdO–Au core may be the active structure for the reaction.

★★★★☆ Cui XJ,Shi F,Deng YQ. Oxidative Imination Of Toluenes Catalyzed By Pd–au/silica Gel Under Mild Reaction Conditions[J]. Chem. Commun.,2012,48:7586-7588.

Complicated and expensive organic ligands are normally essential in fine chemical synthesis at preparative or industrial levels. The synthesis of fine chemicals by using heterogeneous catalyst systems without additive organic ligand is highly desirable but severely limited due to their poor generality and rigorous reaction conditions. Here, we show the results of carbon–nitrogen or carbon–carbonbond formation catalyzed by an Ag/Mo hybrid material with specific Ag6Mo10O33 crystal structure. 48 nitrogen-or oxygen-containing compounds, that is, amines, carboxamides, sulfonamides, and ketones, were successfully synthesized through a borrowing-hydrogen mechanism. Up to 99% isolated yields were obtained under relatively mild conditions without additive organic ligand. The catalytic process shows promise for the efficient and economic synthesis of amine, carboxamide, sulfonamide, and ketone derivatives because of the simplicity of the system and ease of operation.

Keywords: Ag/Mo · amines · carboxamides · ketones · sulfonamides

★★★★☆ Cui XJ,Zhang Y,Shi F,et al. Organic Ligand-free Alkylation Of Amines, Carboxamides, Sulfonamides,and Ketones By Using Alcohols Catalyzed By Heterogeneous Ag/mo Oxides[J]. Chem. Eur. J.,2011,17:1021-1028.

★★★★☆ Cui XJ,Zhang Y,Shi F,et al. Ruthenium-catalyzed Nitro And Nitrile Compounds Coupling With Alcohols: Alternative Route For N-substituted Amine Synthesis[J]. Chem. Eur. J.,2011,17:2587-2591.

The FeCl2/K2CO3 catalyst system was developed successfully for the N-alkylation of sulfonamides with benzylic alcohols via borrowing hydrogen method. XPS analysis gested a possible catalyst cycle between Fe(II) and Fe(0). Under the optimized condition, the scope of the protocol was demonstrated in 21 different alkylation reactions. High yields, in general >90%, are achieved in most cases.

Keywords: Sulfonamide; Alkylation; Alcohol; Iron

★★★★☆ Cui XJ,Shi F,Zhang Y,et al. Fe(ii)-catalyzed N-alkylation Of Sulfonamides With Benzylic Alcohols[J]. Tetrahedron Letters,2010,51:2048-2051.