Here we develop a porous monophoshine polymer supported Pd catalyst (Pd/POL-m-3vPPh3) for hydroaminocarbonylation of aromatic alkenes with amines, showing excellent catalytic activity (up to 97% yield) and Markovnikov selectivity (up to 99%) for producing branched amides. This catalyst exhibits broad substrate compatibility, and is reused for two times with no significant decline in the performance and three times with no significant Pd leaching, as well as applied for the synthesis of naproxen. Here we develop a porous monophoshine polymer supported Pd catalyst (Pd/POL-m-3vPPh3) for hydroaminocarbonylation of aromatic alkenes with amines, showing excellent catalytic activity (up to 97% yield) and Markovnikov selectivity (up to 99%).

A series of Zn-doped nano-Cr2O3 catalysts were prepared by the microwave-assisted combustion method, and the catalysts were successfully applied to the fluorination of 1, 1, 2, 3-tetrachloropropene to synthesize 2-chloro-3, 3, 3-trifluoropropene, and the fluorination of vinylidene chloride to vinylidene fluoride using anhydrous hydrogen fluoride, which is much more efficient than catalyst reported in literatures. By XRD, XPS, and NH3-TPD, it was confirmed that the doping of a small amount of Zn did not have a great influence on the crystal structure of the catalyst but had a great influence on the acidity of the catalyst surface, which increased the number of weak acids and medium acids on the catalyst surface. In addition, the addition of a small amount of Zn could increase the content of high-valent chromium and produce more CrOxFy active centers. As the number of acid sites increases, it provides adsorption centers for chlorine-containing molecules, and the increase of CrOxFy active centers promotes the reaction. They work together to improve the catalytic performance of the catalyst.

氢氨甲基化反应(HAM)是由简单烯烃、胺和合成气一锅法合成有价值胺的方法,具有较高的原子经济效率.然而,4-氨基苯酚作为一种特殊的反应底物,因其同时具有羟基和胺基官能团,在羰基化反应过程中能够选择性地在不同位点发生反应获得不同的产物.因此,我们系统研究了 4-氨基苯酚与烯烃的HAM,通过筛选反应参数,确定了最优反应条件,并通过调控添加剂种类,选择性地在4-氨基苯酚的不同活性位点发生反应.结果表明,以甲醇为溶剂,三(3-甲氧基苯基)膦为配体,RhCl(PPh3)3为催化剂前驱体,合成气压力4MPa(H2 ∶CO=3 ∶1),反应温度100℃,反应时间20 h时,该催化体系具有最高的反应活性.当以CH3COOH作为添加剂时,选择性的4-氨基苯酚的胺基官能团发生氢氨甲基化反应得到产物4-[(2-苯丙基)氨基]苯酚,收率为82％;当以DBU作为添加剂时,得到苯乙酮产物,收率为92％.最后,提出了该反应可能的机理,为4-氨基苯酚的选择性反应提供理论依据.

Vapor fluorination of 1,1,3,3-tetrachloropropene ( HCC-1230za) with HF to trans-1-chloro-3,3,3-trifluoropro-pene ( HCFO-1233zd( E) ) was investigated using the fluorinated Cr2O3 catalysts modified by Al3+, Zn2+, and Co2+. A highly active, selective, and long lifespan Zn/Cr2O3 catalyst was achieved for the first time, where 99.4％ HCC-1230za conversion and 98.2％ HCFO-1233zd (E) selectivity were obtained, and the selectivity to HCFO-1233zd (E) was favored at 200℃and HF/HCC-1230za molar ratio (10 : 1). The catalysts were characterized by XRD, XPS, BET, V70 pyridine adsorption infrared spectrometer and NH3-TPD techniques. The XRD results of catalysts Zn/Cr2O3 indicate that most of the amorphous chromium oxide and finely dispersed microcrystalline phase of Cr2O3 together lead to high activity and long lifespan. The con-version of HCC-1230za and the selectivity to HCFO-1233zd ( E) are related to the specific surface area of the fluorinated ca-talyst, and the higher the specific surface area of the catalyst, the higher selectivity. The XPS spectra of catalyst Zn/Cr2O3 show that exterior Cr2O3 after 118 h reaction formed CrOxFy species. The number and strength of Lewis and Br?nsted acid sites for Zn/Cr2O3 catalysts after 118 h reaction is significantly increased than the fresh one.

Vapor fluorination of 1, 1, 3, 3-tetrachloropropene (HCC-1230za) with HF to trans-1-chloro-3, 3, 3-trifluoropropene (HCFO-1233zd(E)) was investigated using the fluorinated Cr2O3 catalysts modified by Al3+, Zn2+, and Co2+. A highly active, selective, and long lifespan Zn/Cr2O3 catalyst was achieved for the first time, where 99.4% HCC-1230za conversion and 98.2% HCFO-1233zd (E) selectivity were obtained, and the selectivity to HCFO-1233zd (E) was favored at 200 ℃ and HF/HCC-1230za molar ratio (10:1). The catalysts were characterized by XRD, XPS, BET, V70 pyridine adsorption infrared spectrometer and NH3-TPD techniques. The XRD results of catalysts Zn/Cr2O3 indicate that most of the amorphous chromium oxide and finely dispersed microcrystalline phase of Cr2O3 together lead to high activity and long lifespan. The conversion of HCC-1230za and the selectivity to HCFO-1233zd (E) are related to the specific surface area of the fluorinated catalyst, and the higher the specific surface area of the catalyst, the higher selectivity. The XPS spectra of catalyst Zn/Cr2O3 show that exterior Cr2O3 after 118 h reaction formed CrOxFy species. The number and strength of Lewis and Bronsted acid sites for Zn/Cr2O3 catalysts after 118 h reaction is significantly increased than the fresh one.

Fluorine-containing hydrocarbons, which are commonly used as fluoroelastomer functional polymer monomers and fluomresin monomers, refrigerants, aerosol sprays, and foaming agents, were synthesized by the gas phase fluorination method. The method has the advantages of continuous production and avoiding serious corrosion to the reaction kettle, which simplifies the production process and becomes an important method for the production of fluorinated chemical products. This article summarizes catalytic reaction types and reaction mechanisms for the synthesis of HFOs are briefly introduced, and the catalysts used in gas-phase fluorination synthesis are summarized according to the main catalyst components. The traditional preparation methods(such as precipitation methods, etc.) and new preparation methods of various catalysts are introduced ( Such as self-assembly method, solution combustion synthesis method, hard template method, electrospinning method, etc.), as well as catalytic performance, proposed the future development direction of the catalyst.

由于含氟烯烃在自然界易降解、对臭氧层破坏力小、对环境友好的特性,近年来在科研和工业领域得到广泛关注.偏氟乙烯(VDF)和含氟丙烯是重要的含氟烯烃,主要用于合成氟弹性体高分子功能材料的单体和含氟树脂等.我们参照偏氟乙烯的合成发展史,主要介绍了通过催化,热裂解和共裂解方法合成偏氟乙烯过程中使用的催化剂类型、工艺条件和结果对比,综述了近年来偏氟乙烯的主要合成方法,并介绍了通过直接催化氟化法合成含氟丙烯的工艺技术及其可能机理研究进展.

A new efficient catalytic system for one-step synthesis of N-arylated amines, for example, an important intermediate, 4-ethyl-N-[(tetrahydrofuran-3-yl)methyl]aniline, is achieved by using different rhodium precursor and phosphorus ligands catalyzed hydroaminomethylation of aniline and its derivatives with heterocyclic and/or cyclic olefins. By screening the reaction parameters, the optimal reaction conditions are found as follows: methanol as a solvent, PPh3 as a ligand, [Rh(cod)2]BF4 as a catalyst precursor, a P/Rh ratio of 5:1, syngas pressure 4 MPa (H2/CO = 3:1), 100 °C, 20 hours, and no additives. The conversion of aniline reaches >99% and the yield of N-[(tetrahydrofuran-3-yl)methyl]aniline is up to 99% using this catalytic system. Moreover, the reaction of aniline and various cyclic olefins is investigated under the optimal conditions, and excellent conversion and good yields are obtained.

Novel catalytic systems for the Rh-catalyzed hydroformylation of dicyclopentadiene have been developed using tris-H8-binaphthyl monophosphite as ligands containing different ester substituents at the 2'-binaphthyl position (OCOMe, OCOPh, OCOAdamantyl and OCOPhCl). The catalysts exhibited high activity (S/C = 4000, TON = 3286) with good to excellent selectivity towards dialdehydes. Remarkably, the Rh(I) complex bearing the ligands with chlorophenyl ester substituents led to 99.9% conversion and 98.7% selectivity for dialdehydes under relatively mild conditions (6 MPa, 120 °C).

The preparation of new palladium complexes in situ that were composed of a series of chiral diphosphite ligands, which were derived from (1S,2S)-trans-1,2-cyclohexanediol, have been described. It was found that (1S,2S)-bis[(S)-1,1′-binaphthyl-2,2′-diyl]phosphite-cyclohexanediol was the suitable ligand in the Pd-catalyzed allylic alkylation, and up to 75% ee for (E)-dimethyl 2-(1,3-diphenylallyl)malonate was obtained. In compared with the results of the asymmetric allylic alkylation, (1S,2S)-bis[(R)-1,1′-binaphthyl-2,2′-diyl]phosphite-cyclohexanediol was proved to be the most efficient ligand in the Rh-catalyzed asymmetric hydrogenation of dimethyl itaconate and enamides with up to 99% ee. The stereochemically matched combinations between the diol skeleton and diaryl moieties of the ligands were essential for inducing high enantioselectivities in the two transformations. It was found that the sense of the enantiodiscrimination of the products was mainly determined by the configuration of the binaphthyl phosphite moieties.

A novel and practical synthesis of dinotefuran 1, featuring a new access to it from known key intermediate (tetrahydrofuran-3-yl)-methanamine 5, has been achieved through Michael addition reaction of nitromethane to diethyl maleate in 6 steps with 45.5% total yield. This synthesis is scalable and hence has high potential for application to further synthetic elaboration on such new neonicotinoid insecticide dinotefuran 1.

A series of diphosphite ligands, which were derived from D-(-)-tartaric acid, have been synthesized and successfully applied in the Cu-catalyzed asymmetric conjugate addition of organozincs to enones. There was a synergic effect between the stereogenic centers of the D-(-)-tartaric acid skeleton and the axially H8-binaphthyl moieties of ligand 2c. And ligand 2c shows a comparative catalytic performance to ligand 1-N-benzylpyrrolidine-3,4-bis[(S)-1,1′-H8-binaphthyl-2,2′-diyl]phosphite-L-tartaric acid1d derived from L-(+)-tartaric acid. Therefore, for cyclic enones, both enantiomers of the addition products can be obtained in high enantioselectivity (ees up to 96%) by simply selecting ligands 1d or 2c derived from D-(-)-tartaric acid or L-(+)-tartaric acid. Moreover, the sense of enantiodiscrimination of the products was mainly determined by the configuration of the binaphthyl phosphite moieties.

A new series of monodentate phosphites based on the rigid, axially chiral monoesterified H8-BINOL, which are easy to prepare from the readily accessible phosphorylating reagents (Sa)- or (Ra)-1,1′-binaphthyl-2,2′-diylchlorophosphite and (Sa)- or (Ra)-1,1′-H8-binaphthyl-2,2′-diylchlorophosphite, have been synthesized. All ligands were purified on a silica gel column under a nitrogen atmosphere with moderate yields, and were white solids and air-stable at room temperature. These ligands afforded good to excellent enantioselectivities in the Cu-catalyzed 1,4-conjugate addition of 2-cyclohexenone with nucleophiles Et2Zn (96% ee) and with Ph2Zn (65% ee), 2-cyclopentenone with Et2Zn (95% ee), 2-cycloheptenone with Et2Zn (76% ee), and 5,6-dihydro-2H-pyran-2-one with Et2Zn (90% ee). In the Rh-catalyzed asymmetric hydroformylation of styrene, these ligands showed a chemoselectivity of >99% in aldehydes, and a satisfactory branched over linear ratio (96/4). Moreover, the sense of the enantiodiscrimination of the products was mainly determined by the configuration of the BINOL-based or H8-BINOL-based phosphocycle.

A family of the novel chiral helical C-3-symmetric monophosphite ligands has been synthesized from axially chiral (R)- or (S)-H-8-BINOL and PCl3. The performance of these ligands in asymmetric catalysis was evaluated by the Rh-catalyzed asymmetric hydroformylation of styrene, and the Cu-catalyzed asymmetric 1,4-conjugate addition of diethylzinc to acyclic enones. The catalytic hydroformylation of styrene gave rather high conversion (93%), high regioselectivity (b/n=95/5) and low enantioselectivity [28% ee (R)] using ligand (R)-2 in tetrahydrofuran at room temperature. Under the optimal 1,4-conjugate addition of ZnEt2 to chalcone 3a conditions, eleven acyclic enones 4a similar to 4k were all converted smoothly to the 1,4-adducts with high enantiomeric excess. Using Cu(OTf)(2) as catalyst precursor and Et2O as solvent at -20 degrees C, the structure of ligand (R)-3 comprising a partially hydrogenated 2,2'-(1,1'-binaphthyl)-phosphite scaffold and an adamantyl moiety was key factor in improving catalytic activity and the enantioselectivity with up to 98% yield and 72% ee (R). The sense of enantiodiscrimination of the reaction was controlled by the configuration of the diaryl phosphite moieties.

A series of novel chiral diphosphite ligands have been synthesized from (1R,2R)-trans-1,2cyclohexanediol, (1S,25)-trans-1,2-cyclohexanediol, racemic trans-1,2-cyclohexanediol and chlorophosphoric acid diary ester, and were successfully employed in the Cu-catalyzed asymmetric 1,4-conjugate addition of diethylzinc to cyclohexenone with up to 99% ee. It was found that ligand 1,2-bis[(R)-1,1'binaphthy1-2,2'-diyl]phosphitecyclohexanediol 6a derived from racemic diol skeleton can show similar catalytic performance compared with ligand (1R,2R)-bis[(R)-1,1'-binaphthyl-2,2'-diyl]phosphitecyclohexanediol 6a' derived from enantiopure starting material. A significant dependence of stereoselectivity on the type of enone acid the ring size of the cyclic enone was observed. Moreover, the configuration of the products was mainly determined by the configuration of the binaphthyl moieties of diphosphite ligands in the 1,4-addition of cyclic enones. (C)2015 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences. Published by Elsevier B.V. All rights reserved.

Pd/TiN nanocomposite catalysts were fabricated for one-step selective hydrogenation of phenol to cyclohexanone successfully. High conversion of phenol (99%) and selectivity of cyclohexanone (98%) were obtained at 30 degrees C and 0.2 MPa H-2 for 12 h in the mixed solvents of H2O and CH2Cl2. The Pd nanoparticles were stable in the reaction, and no aggregation was detected after four successive runs. The catalytic activity and selectivity depended on slightly the Pd particle sizes. The generality of the catalysts for this reaction was demonstrated by the selective hydrogenation of phenol derivatives, which showed that the catalyst was selective for the formation of cyclohexanone. (C) 2016 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences. Published by Elsevier B.V. All rights reserved.

A series of novel chiral diphosphite ligands was easily prepared in a few steps from commercial (1R,2R)-trans-1,2-cyclohexanediol as the chiral source, and successfully employed in the Rh-catalyzed asymmetric hydrogenation of α,β-unsaturated carboxylic acid derivatives and enamides with up to 99% ee for dimethyl itaconate and enamides and with up to 94% ee for α-dehydroamino acid esters. The stereochemically matched combination of (1R,2R)-trans-1,2-cyclohexanediol backbone and (S)-binaphthyl in the ligand (1R,2R)-bis[(S)-1,1′-binaphthyl-2,2′-diyl]phosphitecyclohexanediol, was essential for inducing high enantioselectivity. Moreover, the sense of enantiodiscrimination of the products was mainly determined by the configuration of the binaphthyl moieties.

手性醛是合成生物活性物质如药物活性分子等的重要中间体,及各种高附加值精细化学品如香料等的起始原料,潜手性烯烃及其衍生物的不对称氢甲酰化是合成光学活性醛的重要方法之一.在烯烃的不对称氢甲酰化中铑与膦形成的催化体系因活性高、选择性好等优点而被广泛应用.主要介绍了近年来几类新型手性磷配体与铑形成的络合物催化剂在不对称氢甲酰化反应中的应用研究结果,如Rh/手性双-3,4-二氮磷杂环戊烷配体(S,S,S)-Bisdiazaphos和(R,S)-NEt-Yanpho络合物催化剂等.