Recycling of homogeneous Pd catalysts using superparamagnetic nanoparticles as novel soluble supports for Suzuki, Heck, and Sonogashira cross-coupling reactions

Recycling of homogeneous catalysts could be achieved by using magnetic nanoparticles and solid-phase beads, but nanoparticle-supported catalysis proceeded much faster than its counterpart on resins.     

分子氧为氧化剂的Au?Ag/TS-1光催化剂协同光催化丙烯气相环氧化

近年来,丙烯环氧化已引起人们广泛的兴趣;然而,大多数过程仍面临分离困难等问题.此外,丙烯转化率和环氧丙烷(PO)的选择性仍然非常低.从环境和经济观点来看,分子氧是丙烯选择性环氧化的理想氧化剂.开发一种气相光催化环氧化方法,即在光能和多相光催化剂存在的情况下,用于化学品生产.因此,本文探讨了通过光催化O2选择氧化丙烯环氧化.传统的制备方法存在环境污染及能耗大等缺点,而利用氧气直接进行光催化丙烯环氧化制备环氧丙烷是相当具有前景的化学品生产途径.本文采用水热法制备了微球状TS-1载体,再通过浸渍还原法制备了不同Au/Ag质量比的Au–Ag/TS-1双金属催化剂.通过X射线衍射、扫描电镜、紫外-可见吸收光谱、透射电镜、X射线光电能谱、荧光光谱和N2吸脱附法等手段对合成的催化剂的组成、形貌和性质进行了研究,通过气相色谱在线分析得到光催化反应结果.结果表明,通过浸渍还原法可以很好的将贵金属分散到载体表面上.对于Au–Ag/TS-1双金属催化剂,当Au/Ag质量比为4/1时,反应温度为443 K时,环氧丙烷生成速率最大(68.3μmol/(g·h)),其选择性达52.3%.对于Au–Ag/TS-1光催化剂,双金属负载有利于O2吸附活化,同时促进了电子的传递,从而抑制电子空穴的复合,有利于氧自由基的形成.结果表明,Au,Ag双金属之间存在协同催化作用,根据实验现象提出了一种可能的反应机理.     

Copper(II) complexes of 2-(pyridine-2-yl)imidazolidine-4-thione derivatives for asymmetric Henry reactions

The preparation of a new series of 2-(pyridine-2-yl)imidazolidine-4-thione derivatives is described. Their corresponding copper(II) complexes were found to be highly enantioselective catalysts for asymmetric Henry reactions (up to 98% ee). Immobilization of these complexes by anchoring onto Merrifield? resin with respect to their use as recyclable catalysts was subsequently performed. The heterogeneous catalysts prepared in this way were tested in the asymmetric Henry reactions and showed high catalytic activity; they can be easily recycled, although their enantioselectivities were only moderate (～50% ee).     

Catalytic asymmetric oxidation of sulfide and styrene derivatives using macroporous resins containing chiral metalloporphyrins (Fe, Ru)

Chiral metalloporphyrin (Fe, Ru) complexes, functionalized with four vinyl groups, have been polymerized with styrene and divinylbenzene (or ethylene glycol) to obtain supported iron and ruthenium complexes. The heterogeneous asymmetric oxidation of sulfides and styrene derivatives was carried out by using these polymers as catalysts. The reaction proceeded under mild conditions and gave sulfoxides and epoxides with good enantiomeric excesses (up to 75–76%). The catalysts keep constant ee values for the recycle tests of up to six times for asymmetric oxidation of styrene derivatives and of up to 14 times for asymmetric oxidation of sulfides with only traces of sulfones.     

Chiral porous hybrid solids for practical heterogeneous asymmetric hydrogenation of aromatic ketones

Chiral porous zirconium phosphonates containing Ru-BINAP-DPEN moieties were synthesized via a molecular building-block approach, and characterized by a variety of techniques including TGA, adsorption isotherms, XRD, SEM, IR, and microanalysis. These hybrid solids were used for enantioselective heterogeneous asymmetric hydrogenation of aromatic ketones with remarkably high ee values of up to 99.2%. These solid catalysts can also be easily recycled and reused for eight times without the loss of activity and enantioselectivity. Ready tunability of such a molecular building-block approach will allow the optimization of these hybrid materials and promise to lead to other practically useful heterogeneous asymmetric catalysts.     

轴不安定性联苯类膦-噁唑啉配体/铱配合物在亚胺不对称氢化反应中的应用

考察了一系列轴不安定性联苯类膦-噁唑啉配体/铱配合物作为手性催化剂用于亚胺类底物的不对称催化氢化反应.结果表明该类催化剂具有很高的催化活性(99%转化率)和较好的对映选择性(75%ee).     

手性β-氨基醇的合成及其催化二乙基锌与醛的不对称加成反应

以烯烃为原料通过Sharpless不对称双羟化等多步反应合成7种手性β-氨基醇, 并将该类化合物用于催化二乙基锌和醛的不对称加成反应. 分别考察了影响对映选择性的催化剂结构、催化剂用量、溶剂、反应温度等各种因素. 当催化剂用量为5%、甲苯溶剂、在－10 ℃下、以(1S,2R)-(＋)-2-氨基-1,2-二苯基乙醇(1b)作催化剂时, 所得仲醇的对映体过量最高为85% ee, 产率高达100%.     

Enantioselective Iron‐Catalyzed Intramolecular Cyclopropanation Reactions

An iron‐catalyzed asymmetric intramolecular cyclopropanation was realized in high yields and excellent enantioselectivity (up to 97 % ee) by using the iron complexes of chiral spiro‐bisoxazoline ligands as catalysts. The superiority of iron catalysts exhibited in this reaction demonstrated the potential abilities of this sustainable metal in asymmetric carbenoid transformation reactions.     

Asymmetric Michael addition reactions of 2-silyloxyfurans catalyzed by binaphthyldiimine-Ni(II) complexes

N,N'-Bis(2-quinolylmethylene)-1,1'-binaphthyl-2,2'-diamine-Ni(II) complex and analogous complexes were found to be efficient chiral Lewis acid catalysts for the asymmetric Michael addition reactions between 2-silyloxyfurans and 3-alkenoyl-2-oxazolidinones, for which asymmetric inductions of up to 97% ee were obtained.     

固载脯氨酸类手性催化剂的制备及在不对称Aldol反应中的催化作用

制备了两种二氧化硅-甲基纤维素-脯氨酸类手性小分子复合催化剂,证明了它们可以在室温下催化不对称Aldol反应.所得产物产率较高,ee值最高能达到86.8%.这些催化剂比较稳定,并具有一定的重复使用的性能.     

手性伯胺催化剂用于顺式选择性的不对称Cross-Aldol反应

基于酸碱作用,将手性伯胺与质子酸原位结合制得有机小分子催化剂,并用于醛与醛的不对称Cross-aldol反应.与一般手性仲胺催化剂不同,该类伯胺催化剂得到的是顺式选择性构型的Cross-aldol产物,其产率达90%,顺反比和ee值分别为9:1和90%.相比而言,采用简单易得的(1S,2S)-(+)-环己二胺即可得到较高选择性的顺式产物.     

手性膦氮配体的合成及其过渡金属配合物对不对称氢转移反应的催化作用

金鸡纳生物碱;手性膦氮配体;不对称氢转移反应     

Development of new asymmetric two-center catalysts in phase-transfer reactions

A new asymmetric two-center phase-transfer catalyst was designed and a catalyst library containing more than 40 new two-center catalysts was constructed. The catalysts were applied in phase-transfer alkylations and Michael additions to afford the corresponding products in up to 93% ee and 82% ee, respectively.     

Enantioselective Hydrogenation of α-Substituted Acrylic Acids Catalyzed by Iridium Complexes with Chiral Spiro Aminophosphine Ligands

Highly active: Iridium complexes with chiral spiro aminophosphine ligands were synthesized and applied as catalysts for the asymmetric hydrogenation of α-substituted acrylic acids. The complexes were highly active catalysts, showing turnover frequencies of up to 6000?h(-1) , and catalyst loadings could be reduced to 0.01?mol?%.     

有机锡在不对称合成中的应用研究进展

金属有机化合物是不对称合成中常用的有机试剂。有机锡试剂易于制备，而且碳-锡键又易于断开，因此它们被广泛应用于有机合成中，当然也是不对称合成常用的试剂之一，是制备某些手性天然产物必备的试剂。由于锡的结构特点，它可以形成四配位、五配位甚至六配位的配合物，这些配合物作为路易斯酸可用作不对称合成中的催化剂、助催化剂。从已报道的文献看，大多数反应的产率及对映体选择性都在中等或中等以上水平，某些已达到了优良的水平。本文综述了有机锡作为反应试剂、催化剂、助催化剂在不对称合成中的应用。     

Asymmetric Cu-catalyzed Henry reaction using chiral camphor Schiff bases immobilized on a macromolecular chain

Immobilized catalysts have attracted chemists’ attention for long time because of convenient recycling, which is very important for some special catalyst even immobilizations accompanying the decrease of catalytic activity and selectivity. Our group focused on the developing chiral catalysts with camphor framework to catalyze various asymmetric reactions for long time. For easily recycling the unique chiral catalysts, a series of polymer catalysts with chiral camphor unit were synthesized by RAFT polymerization. Herein, the performance of the synthesized polymer chiral catalysts was reported by catalyzing asymmetric Henry reaction. After optimizing the reaction conditions, the synthesized chiral polymer catalyst provides a good yield and enantioselectivity to the reaction of p-nitrobenzaldehyde and nitromethane. In the meantime, the recycles and reused properties of synthesized polymer catalysts were examination by the model asymmetric Henry reaction. The catalyzed activities and enantioselectivities did not show obviously decrease until recycling five times.     

Ruthenium(II) Pyrazolyl-Pyridyl-Oxazolinyl Complex Catalysts for the Asymmetric Transfer Hydrogenation of Ketones

Lowering the ketone: Ru(II) complexes containing a chiral pyridyl-based 1H-pyrazolyl-oxazolinyl NNN ligand were synthesized and structurally characterized by X-ray crystallographic studies. These complex catalysts efficiently catalyzed the asymmetric transfer hydrogenation of ketones, reaching up to 99?%?ee for the desired products.     

Highly enantioselective Michael addition of cyclic ketones to chalcones catalyzed by pyrrolidine-based imides

An efficient procedure for asymmetric Michael addition reaction of cyclic ketones with low activated chalcones catalyzed by pyrrolidine-based phthalimide and 1,8-Naphthalimide catalysts was developed. The corresponding products were obtained in high yields with high diastereoselectivities (up to 99:1 dr) and high enantioselectivities (up to 96% ee) under mild conditions.     

Magnetic nanoparticle-supported proline as a recyclable and recoverable ligand for the CuI catalyzed arylation of nitrogen nucleophiles

Magnetic nanoparticle-supported proline ligand was prepared and used for the CuI catalyzed Ullmann-type coupling reactions of aryl/heteroaryl bromides with various nitrogen heterocycles to form the corresponding N-aryl products in good to excellent yields; furthermore, this magnetic nanoparticle-supported proline ligand could be readily separated using an external magnet and reused without significant loss of activity.     

Highly efficient asymmetric Michael addition of aldehydes to nitroalkenes with 4,5-methano-l-proline as organocatalysts

The 4,5-methano-l-prolines were used as chiral organocatalysts in asymmetric Michael addition of aldehydes to nitroolefins. These proline-like catalysts are unique for their rigid bicyclic structure with a cyclopropane and two H atoms attached to the bridgehead C atoms lying on the same side of the ring. They therefore showed high efficiency in asymmetric Michael addition of aldehydes to nitroolefins. Under the optimal conditions, excellent diastereo- and enantioselectivities (up to 97/3 dr and 98% ee) were obtained in high yields for a series of aldehydes and nitroolefins using only 5 mol % catalyst loading. The methodology features easily available catalysts, high catalytic efficiency and environmentally friendly procedures.