椰壳活性炭共价固载钯离子有机络合物催化剂的制备与应用

采用椰壳活性炭为载体,通过20%HNO3氧化处理,Boehm滴定表明活性炭表面羟基含量达0.376 mmol/g.之后分别接枝(MeO)3Si(CH2)3NH2和(MeO)3Si(CH2)3Cl,并成功合成了两种不同类型的含氮双齿配体用来配合钯离子,以FT-IR、XPS、1H NMR、ICP及N2吸附-脱附等手段表征了催化剂制备过程中的各种中间体.在高压反应釜中以苯酚氧化羰基化反应考察了所制催化剂的催化性能.结果表明,在100℃,7.0 MPa及p(CO)/p(O2)=10/1下,二氯甲烷为溶剂,以环庚二胺配体配合的钯离子为催化剂,苯酚转化率及产物碳酸二苯酯(DPC)选择性分别为11.91%、86.82%,对于双氰基配体配合的催化剂,苯酚转化率及产物DPC选择性分别为6.22%及81.02%.     

超临界二氧化碳介质中端炔C—H键与CO_2的羧化反应研究

建立了一个不使用有机溶剂的端炔C—H键羧化新体系:在Ag(I)/DBU(1,8-二氮杂二环十一碳-7-烯)催化体系中,通过超临界二氧化碳与端基炔的羧化反应,以较高产率得到了相应丙炔酸产物.在反应体系中,超临界二氧化碳既是反应物又是反应溶剂;助剂DBU起到了碱、亲核体和共催化剂的作用,并能够明显加快反应速率.筛选出的催化体系具有良好的催化反应活性和底物适应能力,能够实现液态、固态端基炔与超临界二氧化碳的直接羧化反应,为制备功能化丙炔酸类化合物提供了一个环境友好、简单、经济的合成路线.     

Electrocarboxylation of benzyl halides through redox catalysis on the preparative scale

The electrocarboxylation of benzyl halides to the corresponding carboxylic acids through homogeneous charge-transfer catalysis was investigated both theoretically and experimentally to determine the influence of the operative parameters on the yield of the process and on the catalyst consumption. Theoretical considerations, based on fast kinetics of redox catalysis, were confirmed by the electrocarboxylation of 1-phenyl-1-chloroethane catalyzed by 1,3-benzenedicarboxylic acid dimethyl ester performed at a carbon cathode under different operative conditions. We obtained high yields of the target carboxylic acid and experienced a low catalyst consumption by operating with optimized [RX]bulk/[CO2]bulk and [RX]bulk/[catalyst] ratios.     

Site-Selective,Remote sp3 C−H Carboxylation Enabled by the Merger of Photoredox and Nickel Catalysis

A photoinduced carboxylation of alkyl halides with CO₂ at remote sp³ C−H sites enabled by the merger of photoredox and Ni catalysis is described. This protocol features a predictable reactivity and site selectivity that can be modulated by the ligand backbone. Preliminary studies reinforce a rationale based on a dynamic displacement of the catalyst throughout the alkyl side chain.     

Electrochemically Activated Reaction of Benzoyl Halides with Carbon Dioxide

The electrochemical activation and carboxylation of benzoyl halides (benzoyl bromide, chloride, and fluoride) were studied. It was found that the yield of phenylglyoxylic acid increases from zero to 88% in the transition from benzoyl fluoride to the chloride and bromide. The effect of the nature of the halogen atom in the benzoyl halide and also the nature of the supporting electrolyte and the electrode material on the electrochemical reduction and carboxylation of benzoyl halides was studied.     

2‐Arylsilacyclobutane as a Latent Carbanion Reacting with CO2

An electronically neutral 2‐arylsilacyclobutane generates a nucleophilic carbanion at room temperature through cleavage of the benzylic C?Si bond when simply dissolved in polar aprotic solvents such as N,N‐dimethylformamide (DMF). The nucleophilic species is capable of capturing carbon dioxide to furnish a silalactone. The carboxylation reaction is unique in that no additional activating agents are required.     

Electrosynthesis of cinnamic acid by electrocatalytic carboxylation of phenylacetylene in the presence of [NiII(Me4-NO2Bzo[15]tetraeneN4)] complex: An EC′CCC′C mechanism

A Ni(II) complex, [Ni^II(Me₄-NO₂Bzo[15]tetraeneN₄)], was used for electrocatalytic reduction of CO₂ in acetonitrile solvent. Then, the reduced form of CO₂ (CO₂^?) was used for selective carboxylation of phenylacetylene to produce cinnamic acid at room temperature. The potential of the process is significantly less negative in comparison with those reported earlier. Using sacrificial magnesium electrode as anode, controlled potential coulometry was carried out in an undivided glass cell. The spectral characterizations of FTIR, ¹H NMR, and ¹³C NMR demonstrated that cinnamic acid was the main product of the electrolysis. With respect to other catalysts, which have been previously reported in the literature, application of the Ni(II) complex in carboxylation of unsaturated compounds has three advantages: (1) the selectivity in the production of cinnamic acid; (2) more increase in the reduction current indicating that the carboxylation of phenylacetylene is fast; and (3) the potential shift of electrocatalytic reduction of CO₂ to less negative values showing that the Ni(II) complex has an excellent electrocatalytic activity for CO₂ reduction. According to the voltammetric and coulometric results, an EC′CCC′C mechanism was proposed for the electrocatalytic synthesis of cinnamic acid.     

CO2-Transfer durch Metallphenolate: N-Methyl-ε-carolactam/Natriumphenolat als selektives Reagenz für Carboxylierungsreaktionen

CO₂ Transfer by Metal Phenoxides: N-Methyl-ε-caprolactam/Sodium Phenoxide as a Selective Reagent for Carboxylation Reactions Carboxylation reaction of aceton and other substrates with active C H bonds can be carried out selectively by complexes of sodium phenoxide with N-methyl-ε-caprolactam („NMC”︁) and CO₂. With aceton 3-keto-glutaric acid is formed in 85% yield upon hydrolysis. X-Ray structural analysis of the tetrameric [(NMC)Na(OPh)]₄ shows that sodium- and oxygen ions of the phenoxide occupy the positions of a cubus. NMC acts as monodendate ligand, the oxygen atoms of the phenoxide are tridendate bridging ligands. The lithium compound has a similar structure. The complex solved in NMC takes up 0.5 mol CO₂ per mol Natrium which at room temperature and normal pressure is transformed to aceton.     

Facile electrochemical transformation of diazonium salts into carboxylic acids

The electrolyses of aryldiazonium tetrafluoroborates in dry DMF and Bu₄NHSO₄ as solvent-supporting electrolyte system, in the presence of CO₂ led to the corresponding arylcarboxylic acids in very good yields.