应用QSPR方法计算炔烃的摩尔体积

根据分子中基团的特性和连接性 ,通过探讨炔烃的摩尔体积与其分子结构之间的定量关系 ,发展一种直接根据分子结构计算炔烃摩尔体积的方法 .该方法将基团贡献法和拓扑方法有机地结合在一起 ,具有基团贡献法适用范围广和拓扑方法计算结果可靠的特点 .对 84种炔烃 (C5到C40 )的计算结果表明 ,摩尔体积计算值与实验值的一致性令人满意 ,平均误差 0 .6 0 % .

C–X(X = Cl, Br, I) bond dissociation energy as a descriptor for the redispersion of sintered Au/AC catalysts

Disintegration or redispersion of supported sintered gold nanoparticles （Au NPs） in the presence of alkyl halide can give catalyst regeneration or redispersion of sintered Au catalysts. The selectivity of alkyl halides, temperature and size distributions were investigated to elucidate the redispersion of Au NPs during halide-induced decomposition. This study proved that the alkyl halide induced the redispersion of sintered Au NPs which depended on the R-X （X = I, Br, CI） bond dissociation energy （BDE） and thus provided a simple descriptor for the regeneration of inactive supported Au cata- lysts. A correlation between the BDE of R-X and dispersion efficiency was established. The tendency for disintegration and redispersion followed the R-X BDE of the alkyl halide. Compared to alkyl chlorides and bromides, iodides were more efficient for redispersing sintered Au NPs. As a descriptor, the BDE of R-I played a crucial role in particle redispersion. These findings provided in- sights into the mechanism of organic halide-induced Au NP disintegration and the effect of the hal- ide type on the redispersion of sintered catalysts.

Efficient visible light initiated hydrothiolations of alkenes/alkynes over Ir_(2)S_(3)/ZnIn2S4:Role of Ir_(2)S_(3)

The hydrothiolations of alkynes/alkenes with thiols is an atom-economic and thus attractive method for the constructions of C‒S bonds.Here Ir_(2)S_(3)/ZnIn_(2)S_(4)nanocomposites with varied Ir_(2)S_(3)loadings were obtained by one-pot solvothermal method from ZnCl_(2),InCl_(3)and thioacetamide with IrCl_(3).The loading of Ir_(2)S_(3)on the surface of ZnIn_(2)S_(4)promoted the hydrothiolations of alkenes and alkynes,with an optimum performance observed over 0.5 mol%Ir_(2)S_(3)/ZnIn_(2)S_(4)nanocomposite.Based on the studies on the performance of several other cocatalysts(MoS2,NiS and Pd)loaded ZnIn_(2)S_(4)and the EIS analyses,it was proposed that the superior performance over Ir_(2)S_(3)/ZnIn_(2)S_(4)nanocomposite can be ascribed to an improved efficiency on the photogeneration of the thiyl radicals by loading Ir_(2)S_(3)as well as its inactivity for photocatalytic hydrogen evolution,a side reaction in the light initiated hydrothiolation reaction over ZnIn_(2)S_(4).This study not only demonstrates an efficient and green strategy to synthesize thiolated products under visible light based on semiconductor photocatalysis,but also provides some guidances for the design and development of photocatalytic systems for light induced organic syntheses.

加成型液体硅橡胶用铂配合物催化剂

介绍了加成型液体硅橡胶用铂配合物催化剂,包括铂-乙烯基硅氧烷配合物的制备及改进方法、包埋型铂-乙烯基硅氧烷配合物的制备方法(喷雾干燥法、水分散液法、热熔法)、铂-乙炔基(铂-炔醇、环二烯烃铂-炔醇、三有机磷铂-炔醇)配合物的制备方法,以及醇改性氯铂酸(辛醇改性氯铂酸、乙醇改性氯铂酸)的配制。

Visible light promoted difunctionalization reactions of alkynes

Visible light promoted difunctionalization of alkynes is reviewed. The difunctionalization reaction is achieved by different reagents. Radicals such as carbon(sp3), carbon(sp2), and other heteroatom(P, S, N, Se, O, and halide) radicals initiated by visible light can undergo radical addition to a carbon-carbon triple bond. Upon further transformation, the desired difunctionalized products are obtained. Some organometallic complexes can be activated by visible light;the difunctionalization of alkynes is catalyzed by these species. Other reagents like 1,3-dipole precursors could also react with alkynes to give difunctionalization products;here, the 1,3-dipole derivatives are obtained by visible light photocatalysis. So far, the strategy has been succeeded in the formation of C–C bonds and C–X bonds. Several valuable chemical skeletons have been constructed under mild conditions. However, high regio-and stereoselectivities in some direct difunctionalization methodologies are yet to be achieved.

Highly active binuclear Cu(Ⅱ) catalyst bearing an unsymmetrical bipyridine-pyrazole-amine ligand for the azide-alkyne cycloaddition reaction

Ligands containing NH groups often show special characteristics.In this paper,a well-defined dinuclear Cu（II） complex bearing an unsymmetrical bipyridine-pyrazole-amine ligand was synthesized by the condensation of N–H to release H2O.Using sodium L-ascorbate as a reductant,the binuclear complex showed excellent activity in 1,3-dipolar cycloaddition reactions between alkynes and azides to obtain 1,4-disubstituted triazoles in 95%–99% isolated yields.

Selectivity control in alkyne semihydrogenation:Recent experimental and theoretical progress

Researchers have been attempting to characterize heterogeneous catalysts in situ in addition to correlating their structures with their activity and selectivity in spite of many challenges.Here,we review recent experimental and theoretical advances regarding alkyne selective hydrogenation by Pd‐based catalysts,which are an important petrochemical reaction.The catalytic selectivity for the reaction of alkynes to alkenes is influenced by the composition and structure of the catalysts.Recent progress achieved through experimental studies and atomic simulations has provided useful insights into the origins of the selectivity.The important role of the subsurface species(H and C)was revealed by monitoring the catalyst surface and the related catalytic performance.The atomic structures of the Pd catalytic centers and their relationship with selectivity were established through atomic simulations.The combined knowledge gained from experimental and theoretical studies provides a fundamental understanding of catalytic mechanisms and reveals a path toward improved catalyst design.

Unveiling subsurface hydrogen inhibition for promoting electrochemical transfer semihydrogenation of alkynes with water

Highly selective electrocatalytic semihydrogenation of alkynes to alkenes with water as the hydrogen source over palladium-based electrocatalysts is significant but remains a great challenge because of the excessive hydrogenation capacity of palladium.Here,we propose that an ideal palladium catalyst should possess weak alkene adsorption and inhibit subsurface hydrogen formation to stimulate the high selectivity of alkyne semihydrogenation.Therefore,sulfur-modified Pd nanowires(Pd-S NWs)are designedly prepared by a solid-solution interface sulfuration method with KSCN as the sulfur source.The introduction of S weakens the alkene adsorption and prevents the diffusion of active hydrogen(H^(*))into the Pd lattice to form unfavorable subsurface H^(*).As a result,electrocatalytic alkyne semihydrogenation is achieved over a Pd-S NWs cathode with wide substrate scopes,potential-independent up to 99%alkene selectivity,good fragile groups compatibility,and easily synthesized deuterated alkenes.An adsorbed hydrogen addition mechanism of this semihydrogenation reaction is proposed.Importantly,an easy modification of commercial Pd/C by in situ addition of SCN–enabling the gram-scale synthesis of an alkene with 99%selectivity and 95%conversion highlights the promising potential of our method.

On the comparable activity in plasmonic photocatalytic and thermocatalytic oxidative homocoupling of alkynes over prereduced copper ferrite

Despite of extensive attention on the copper-based heterogeneous oxidative homocoupling of alkynes(OHA)to 1,3-diynes,the photocatalytic OHA is scarcely investigated.By screening copper-containing spinel catalysts,we discovered that a prereduced copper ferrite(CuFe2O4)not only can catalyze the thermocatalytic OHA but also is efficient for the photocatalytic OHA under visible light irradiation.It is found that the sol-gel combustion(SG)method and the partial reduction at 250 ℃ can result in the optimal CuFe2O4-SG-250 catalyst showing high activity and stability.Surface oxidized Cu2O is evidenced to be the active species for the thermocatalytic OHA,whereas metallic copper nanopaticles(CuNPs)are identified as the active sites for the photocatalytic OHA.The efficiency of photocatalytic OHA at ambient temperature is comparable to that of thermocatalytic OHA at 120 ℃,and the CuFe2O4-SG-250 catalyst can be magnetically separated and reused at least five times.The localized surface plasmon resonance effect of CuNPs contributes to visible light-induced photocatalytic OHA.

Synthesis and Fluorescence Spectra of Triazolylcoumarin Fluorescent Dyes

Much attention is devoted to fluorescent dyes especially those with potential in versatile applications.Reactions under "click" conditions between nonfluorescent 3-azidocoumarins and terminal alkynes produced 3-(1,2,3-triazol-1-yl)coumarins,a novel type of fluorescent dyes with intense fluorescence.The structures of the new coumarins were characterized by 1H NMR,MS,and IR spectra.Fluorescence spectra measurement demonstrated excellent fluorescence performance of the triazolylcoumarins and this click reaction is a promising candidate for bioconjugation and bioimaging applications since both azide and alkynes are quite inert to biological systems.

Numerical Investigation for the Effect of Unsaturated Aliphatic Hydrocarbons Addition on Precursors on Carbon Black

To investigate the effect of unsaturated aliphatic hydrocarbons on PAHs （polycyclic aromatic hydrocarbons） formation, numerical analysis using detailed reaction mechanism is performed. For the carbon black produced by benzene feedstock, three kinds of unsaturated aliphatic hydrocarbons （acetylene, diacetylene, and vinylacetylene） are added. The detailed reaction mechanism which is proposed by Wang and Frenklach is consisted by 527 reactions and 99 chemical species. The formations of PAHs and nuclei are promoted by unsaturated aliphatic hydrocarbons addition. There exits optimal benzene/acetylene ratio （XA/XB = 0.50）, benzene/diacetylene mixture ratio （XD/XB = 0.60）, benzene/vinyl-acetylene mixture ratio （XV/XB = 0.25）. The formation of nuclei is most promoted by acetylene addition, and the benzene/acetylene mixture ratio is 0.50.

氢自由基引发的1,2-炔基迁移

报道了一类新颖的Fe(Ⅲ)介导的形式上的非活性烯烃的氢炔化反应.该反应利用Fe(acac)3与苯硅烷反应能原位产生氢自由基的特性实现了氢自由基诱导的1,4-烯炔的分子内1,2-炔基迁移,合成了一系列α-炔酮类化合物,产率中等到良好.基于实验结果及文献报道,提出了可能的反应机理,其涉及氢自由基加成、3-exo-dig环化(反鲍德温规则)和C—C键的断裂重组等.此外,该反应具有良好的官能团兼容性,如雌酮衍生的1,4-烯炔也能成功参与该反应.

Iron-mediated cross dehydrogenative coupling(CDC) of terminal alkynes with benzylic ethers and alkanes

Iron-mediated sp-sp3 C-C bond formation through the cross dehydrogenative coupling(CDC) of terminal alkynes with benzylic ethers or alkanes has been developed.The inexpensive iron salt is used as the catalyst to make this transformation environmentally benign.Iron-mediated sp-sp3 C-C bond formation through the cross dehydrogenative coupling(CDC) of terminal alkynes with benzylic ethers or alkanes has been developed.The inexpensive iron salt is used as the catalyst to make this transformation environmentally benign.

Syntheses of N-sulfonyl-N,N-disubstituted amidines via a three-component free-radical coupling reaction of tertiary amines and arenesulfonyl azides with terminal alkynes

A facile and efficient synthesis of N-sulfonyl-N,N-disubstituted amidines has been achieved via a CuI-catalyzed three-component free-radical coupling reaction of tertiary amines and arenesulfonyl azides with terminal alkynes in the presence of azodiisobutyronitrile(AIBN).The reaction mechanism of this reaction has also been studied.

Photoredox-catalyzed [4+2] annulation of cyclobutylanilines with alkenes, alkynes, and diynes in continuous flow

Continuous flow has recently emerged as a powerful enabling technology that greatly improves many reactions' efficiency. Here, we apply the technology to intermolecular [4+2] annulation of cyclobutylanilines with alkenes, alkynes, and diynes by photoredox catalysis. An across-the-board improvement in the annulation's efficiency is noticed. Moreover, a gram-scale annulation is successfully demonstrated in continuous flow using a much lower catalyst loading.

Rhodium(Ⅲ)-catalyzed [3+2] annulative coupling between oximes and electron-deficient alkynes

Rhodium(III)-catalyzed coupling between ketoximes and alkynes via C–H activation and annulation typically followed the[4+2]selectivity to afford isoquinolines.By designing alkynes bearing a highly electron-withdrawing group and under substrate control,we have successfully switched the selectivity of the coupling between oximes and alkynes to the alternative[3+2]annulation,leading to the efficient synthesis of indenamines.This process features good regioselectivity for both substrates,high efficiency,broad substrate scope,and excellent functional group tolerance.

Free radical fluoroalkylation of terminal alkenes and alkynes with iododifluoromethanesulfonamides

Free radical fluoroalkylation of terminal alkenes and alkynes with iododifluoromethanesulfonamides has been successfully achieved.It was found that both the catalytic amount of sodium dithionite (Na2S2O4) and the stoichiometric amount of triethylborane (Et3B)/air can efficiently initiate the current free-radical atom transfer reaction.