Binuclear Enamino-Oxazolinate Rare-Earth Metal Complexes: Synthesis and Their Catalytic Performance in Isoprene Polymerization.

We have synthesized a series of binuclear rare-earth metal complexes bearing the newly designed enamino-oxazolinate ligands that feature bridging para-phenyl, meta-phenyl, 1,5-naphthalenyl, and 1,5-anthracenyl moieties. NMR and X-ray diffraction analyses confirmed the binuclear structures of the obtained complexes with two enamino-oxazolinate-metal units located at a trans position against the bridged aryl plane. After activation by [Ph3C][B(C6F5)4], all the rare-earth metal complexes served as efficient catalysts for isoprene polymerization, producing polymers with high cis-1,4 regularity (up to 96.1%) and high molecular weight. The steric and electronic effects exerted on the active metal centers, as well as the radius of metal centers, were the major contributing factors for determining both the catalytic activity and cis-1,4-selectivity of the binuclear catalytic systems. Compared to its mononuclear analogue, the binuclear yttrium catalytic system with a para-phenyl bridge exhibited a higher thermostability and catalytic efficiency during polymerization, revealing a special binuclear effect in this binuclear catalytic system.

Intramolecular Carboamination of Aminodienes to N-Heterocycles via C-N Bond Activation.

The catalytic transformation of ubiquitous but inert C-N bonds is highly appealing in synthetic chemistry, but the efficient cleaving inert C-N bond and simultaneous incorporation of both the cleaved C-moiety and N-moiety into the desired products has been a long-standing formidable challenge so far. Here, we developed a radical-addition triggered cyclization and C-N bond cleavage process enabled by the unique I2 /Ni or benzyl halide/Ni-catalytic system, allowing the formal insertion of diene into the inert C-N bond. This reaction features high atom economy and enables an expedient annulative carboamination of aminodienes to diverse pyrrolidines, piperidines, and tetrahydroisoquinolines. Mechanistic studies have revealed that the reaction is initiated via the generation of a benzyl radical and the formation of quaternary ammonium salt is key for the C-N bond cleavage.

Copper-Catalyzed Claisen Rearrangement with AIBN and Allylic Alcohols.

A novel and succinct method for the synthesis of N-cyanomethyl amides from allylic alcohols with AIBN as the nitrile source is developed. Owing to the coordination effect with the copper catalyst, a ketenimine intermediate is formed via couplings of isobutyronitrile radicals. The copper-activated ketenimine could subsequently be intercepted by allylic alcohols and undergo Claisen rearrangement to furnish N-cyanomethyl amides. Further functional group transformations of the N-cyanomethyl amide products are also described.

Polymerization of Bio-Derived Conjugated Dienes with Rare-Earth-Metal Complexes.

The reliance of both our life and industry on fossil resource and the alarming accumulation of polymeric materials in the environment have presented huge challenges to sustainable society. Nowadays, utilization of renewable monomers as building blocks for polymeric materials has emerged as a hot topic and increasingly gained attention from chemists. As a class of biomass with abundance and low cost, terpenes are typical hydrocarbon-rich natural compounds, and some of them, such as myrcene and farnesene, are inherently suitable for coordination polymerization. In this review, we focus on the rare-earth metal catalyzed highly regio- and stereoselective polymerization of bio-based conjugated dienes, especially the ones from terpene-derived compounds with or without modifications. This review also discusses the future direction on the modification of these bio-based conjugated dienes.

Highly regioselective and diastereodivergent aminomethylative annulation of dienyl alcohols enabled by a hydrogen-bonding assisting effect.

A ligand-controlled palladium-catalyzed highly regioselective and diastereodivergent aminomethylative annulation of dienyl alcohols with aminals has been established, which allows for producing either cis- or trans-disubstituted isochromans in good yields with complete regioselectivity and good to excellent diastereoselectivity. Moreover, the chiral cis-products were also obtained in good yields with up to 94% ee by using a chiral phosphinamide as the ligand. Mechanistic studies revealed that the hydroxyl group plays a key role in facilitating the Pd-catalyzed Heck insertion regioselectively taking place across the internal C[double bond, length as m-dash]C bond of conjugated dienes.

Asymmetric Aminomethylative Etherification of Conjugated Dienes with Aliphatic Alcohols Facilitated by Hydrogen Bonding.

The asymmetric construction of allylic C-O bonds with primary or secondary aliphatic alcohols remains a substantial challenge in Pd-catalyzed allylation chemistry. Here, we report the development of an additive-free, palladium-catalyzed asymmetric aminomethylative etherification of conjugated dienes that enables the efficient, asymmetric O-allylation of primary and secondary aliphatic alcohols as well as water. Mechanism studies revealed that the hydrogen-bonding interaction between the alcohol and the in situ introduced aminomethyl moiety is critical to facilitate the nucleophilic addition of the alcohol to the π-allylpalladium species, which opened up the possibility of using aliphatic alcohols and water as nucleophilic substrates. This reaction tolerates a broad range of functional groups and shows remarkable regioselectivities and uniformly high enantioselectivities, which provides a direct and rapid approach to optically pure allylic 1,3-amino ethers and 1,3-amino alcohols from simple starting materials.

Catalytic Claisen Rearrangement by Intercepting Ketenimines with Propargylic Alcohols: A Strategy to Generate and Transform Ketenimines from Radicals.

An efficient strategy for facilitating the cross-coupling of two radicals has been established via the coordination of a radical with a metal catalyst. This strategy provides a remarkable ability to harness the reactivity of nitrile-containing azoalkanes and enables a novel cascade reaction with nitrile-containing azoalkanes and propargylic alcohols to be established. By using this reaction, a range of acetylenic and allenic amides were obtained that provides a versatile platform for further derivatizations.

Investigation of the interaction of aurantio-obtusin with human serum albumin by spectroscopic and molecular docking methods.

The interaction between human serum albumin (HSA) and aurantio-obtusin was investigated by spectroscopic techniques combined with molecular docking. The Stern-Volmer quenching constants (KSV ) decreased from 8.56 × 105  M-1 to 5.13 × 105  M-1 with a rise in temperatures from 289 to 310 K, indicating that aurantio-obtusin produced a static quenching of the intrinsic fluorescence of HSA. Time-resolved fluorescence studies proved again that the static quenching mechanism was involved in the interaction. The sign and magnitude of the enthalpy change as well as the entropy change suggested involvement of hydrogen bonding and hydrophobic interaction in aurantio-obtusin-HSA complex formation. Aurantio-obtusin binding to HSA produced significant alterations in secondary structures of HSA, as revealed from the time-resolved fluorescence, Fourier transform infrared (FT-IR) spectroscopy, three-dimensional (3D) fluorescence and circular dichroism (CD) spectral results. Molecular docking study and site marker competitive experiment confirmed aurantio-obtusin bound to HSA at site I (subdomain IIA).

Probing the binding properties of dicyandiamide with pepsin by spectroscopy and docking methods.

Dicyandiamide (DCD), considered to be a nitrification inhibitor, poses threat to human's health with exposure from milk, infant formula and other food products. In this work, DCD was investigated for its binding reaction with pepsin using spectroscopy and docking methods. Fluorescence experiments indicated DCD quenched the fluorescence of pepsin through a static process. Thermodynamic analysis of the binding data (ΔH0 = -21.72 kJ mol-1 and ΔS0 = 17.61 J mol-1 K-1) suggested the involvement of hydrophobic and hydrogen bonding in the complex formation. The pepsin interacted with DCD at a hydrophobic cavity, leading to a conformational changes in the pepsin, as revealed from UV-vis absorption, Fourier transform infrared, the time-resolved fluorescence, three-dimensional fluorescence and circular dichroism spectral results.

Chloroacetate Promotes and Participates in the Oxidative Annulation of Pyridines/Isoquinoline by Using Oxygen as the Oxidant.

The aerobic oxidative annulation of chalcones, pyridines/isoquinoline and ethyl chloroacetate to indolizines was achieved by cascade reaction. Various functional groups on chalcones were tolerated. And different pyridines derivatives could also be suitable substrates. Ethyl chloroacetate is an essential component in participating of the oxidative annulation process. Overall, this protocol is very practical and efficient by using molecular oxygen as oxidant with high selectivity for the annulation product.

Evaluation of the binding of perfluorinated compound to pepsin: Spectroscopic analysis and molecular docking.

In this paper, we investigated the binding mode of perfluorooctanoic acid (PFOA) and perfluorononanoic acid (PFNA) to pepsin using spectroscopies and molecular docking methods. Fluorescence quenching study indicated that their different ability to bind with pepsin. Meanwhile, time-resolved fluorescence measurements established that PFOA and PFNA quenched the fluorescence intensity of pepsin through the mechanism of static quenching. The thermodynamic parameters showed that hydrophobic forces were the main interactions. Furthermore, UV-vis, FTIR, three-dimensional fluorescence and molecular docking result indicated that PFCs impact the conformation of pepsin and PFOA was more toxic than PFNA. The conformational transformation of PFOA/PFNA-pepsin was confirmed through the quantitative analysis of the CD spectra. The present studies offer the theory evidence to analyze environmental safety and biosecurity of PFCs on proteases.

Interaction of human serum albumin with novel imidazole derivatives studied by spectroscopy and molecular docking.

This study was a detailed characterization of the interaction of a series of imidazole derivatives with a model transport protein, human serum albumin (HSA). Fluorescence and time-resolved fluorescence results showed the existence of a static quenching mode for the HSA-imidazole derivative interaction. The binding constant at 296 K was in the order of 10(4) M(-1), showing high affinity between the imidazole derivatives and HSA. A site marker competition study combined with molecular docking revealed that the imidazole derivatives bound to subdomain IIA of HSA (Sudlow's site I). Furthermore, the results of synchronous, 3D, Fourier transform infrared, circular dichroism and UV-vis spectroscopy demonstrated that the secondary structure of HSA was altered in the presence of the imidazole derivatives. The specific binding distance, r, between the donor and acceptor was obtained according to fluorescence resonance energy transfer.

Synthesis of imidazole derivatives and the spectral characterization of the binding properties towards human serum albumin.

Small molecular drugs that can combine with target proteins specifically, and then block relative signal pathway, finally obtain the purpose of treatment. For this reason, the synthesis of novel imidazole derivatives was described and this study explored the details of imidazole derivatives binding to human serum albumin (HSA). The data of steady-state and time-resolved fluorescence showed that the conjugation of imidazole derivatives with HSA yielded quenching by a static mechanism. Meanwhile, the number of binding sites, the binding constants, and the thermodynamic parameters were also measured; the raw data indicated that imidazole derivatives could spontaneously bind with HSA through hydrophobic interactions and hydrogen bonds which agreed well with the results from the molecular modeling study. Competitive binding experiments confirmed the location of binding. Furthermore, alteration of the secondary structure of HSA in the presence of the imidazole derivatives was tested.

Study of interaction between human serum albumin and three phenanthridine derivatives: fluorescence spectroscopy and computational approach.

Over the past decades, phenanthridine derivatives have captured the imagination of many chemists due to their wide applications. In the present work, the interaction between phenanthridine derivatives benzo [4,5]imidazo[1,2-a]thieno[2,3-c]quinoline (BTQ), benzo[4,5]imidazo[1,2-a]furo[2,3-c]quinoline (BFQ), 5,6-dimethylbenzo[4,5]imidazo[1,2-a]furo[2,3-c]quinoline (DFQ) and human serum albumin (HSA) were investigated by molecular modeling techniques and spectroscopic methods. The results of molecular modeling simulations revealed that the phenanthridine derivatives could bind on both site I in HSA. Fluorescence data revealed that the fluorescence quenching of HSA by phenanthridine derivatives were the result of the formation of phenanthridine derivatives-HSA complex, and the binding intensity between three phenanthridine derivatives and HSA was BTQ>BFQ>DFQ. Thermodynamics confirmed that the interaction were entropy driven with predominantly hydrophobic forces. The effects of some biological metal ions and toxic ions on the binding affinity between phenanthridine derivatives and HSA were further examined.