Synthesis of 3,4,5-trisubstituted phenols via Rh(III)-catalyzed alkenyl C-H activation assisted by phosphonium cations.

An efficient method for the construction of various 3,4,5-trisubstituted phenol derivatives has been achieved via the Rh(III)-catalyzed coupling of phosphonium cations with internal alkynes. This protocol shows good substrate compatibility, as an array of structurally and electronically diverse phosphonium compounds react efficiently with up to 87% yield.

Rh(III)-catalyzed [4 + 1] cyclization of aryl substituted pyrazoles with cyclopropanols via C-H activation.

A rhodium-catalyzed formal [4 + 1]-cyclization reaction of aryl substituted pyrazoles with cyclopropanols via C-H bond activation/cyclization processes to selectively construct a series of carbonyl functionalized pyrazolo[5,1-a]isoindoles is described. The reaction features good functional group compatibility and a broad substrate scope with respect to both cyclization components with up to 84% yields. Mechanistic studies indicated that the C-H cleavage might be the rate-determining step in this transformation.

Iron-catalysed reductive coupling for the synthesis of polyfluorinated compounds.

Herein we reported the use of Earth-abundant iron as the catalytic metal in the presence of Mn to induce difluorobromoacetates to form carbon radicals, which reacted with trifluoromethyl olefins followed by ß-F elimination to generate the corresponding gem-difluoroolefins. The cross-electrophile coupling displayed excellent functional group tolerance and broad substrate scope under mild reductive conditions, affording a large number of polyfluorinated compounds, which could be further transformed to other valuable molecules.

Phenanthroline-based microporous organic materials for removal of Cu(II) from aqueous solution and reutilization of spent adsorbent as catalysts.

Microporous organic polymers (MOPs) possessing large specific surface area with high stability are suitable adsorbent to remove contaminants from water, such as organic pollutant and heavy metal contaminants. Herein, a phenanthroline-based microporous organic polymer (Phen-MOP) has been synthesized through the coupling between benzene and 1,10-phenanthroline. The adsorption kinetics and thermodynamics were investigated. This Phen-MOP exhibited good adsorption efficiency for removal of Cu(II) from water with high structural stability and reusability. The maximum removal efficiency could reach to 98.47% at a Cu(II) concentration of 20 mg/L, pH = 7, 25 °C. It was found by investigating the adsorption isotherms that the maximum adsorption capacity Qm was 128.53 mg/g. Interestingly, after the adsorption of Cu(II), the resulting Phen-MOP-Cu can serve as an efficient heterogeneous catalyst for the Ullmann-type reaction. The structure and composition of the Phen-MOP-Cu were characterized by Fourier transform infrared (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), Brunauer-Emmett-Teller (BET), scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS). The results indicated that this catalyst possessed immense specific surface area, large pore volume and high stability. The catalyst was easily recyclable and did not significantly lose catalytic activity after being reused six times.

Light-driven transition-metal-free direct decarbonylation of unstrained diaryl ketones via a dual C-C bond cleavage.

The cleavage and formation of carbon-carbon bonds have emerged as powerful tools for structural modifications in organic synthesis. Although transition-metal-catalyzed decarbonylation of unstrained diaryl ketones provides a viable protocol to construct biaryl structures, the use of expensive catalyst and high temperature (>140 oC) have greatly limited their universal applicability. Moreover, the direct activation of two inert C - C bonds in diaryl ketones without the assistance of metal catalyst has been a great challenge due to the inherent stability of C - C bonds (nonpolar, thermo-dynamically stable, and kinetically inert). Here we report an efficient light-driven transition-metal-free strategy for decarbonylation of unstrained diaryl ketones to construct biaryl compounds through dual inert C - C bonds cleavage. This reaction featured mild reaction conditions, easy-to-handle reactants and reagents, and excellent functional groups tolerance. The mechanistic investigation and DFT calculation suggest that this strategy proceeds through the formation of dioxy radical intermediate via a single-electron-transfer (SET) process between photo-excited diaryl ketone and DBU mediated by DMSO, followed by removal of CO2 to construct biaryl compounds.

Umpolung carbonyls enable direct allylation and olefination of carbohydrates.

Mother Nature has its own arts to build a vast number of carbohydrates; however, there is still a lack of tools for selective functionalization of native carbohydrates through C─C bond formation. Such a long-standing challenge for the synthetic community lies into the intrinsic problems related to the innate properties of carbohydrates, e.g., the ease to oligomerization or polymerization, the difficulty of chemoselectivity control in the presence of multiple hydroxyl groups, the great challenge to retain the multiple chiral centers during the transformation, etc. Here, by applying an umpolung strategy of carbohydrate carbonyls, we report a direct deoxygenative allylation and olefination of carbohydrates to tackle the abovementioned issues. The reaction is compatible with a wide range of natural carbohydrates, providing a direct synthetic method to use carbohydrates as multiple C-centered chiral synthons to achieve C─C bond cross-coupling reactions. Furthermore, the synthetic applicability is demonstrated by late-stage modifications of natural products and pharmaceutical derivatives.

Metal-organic framework grown in situ on chitosan microspheres as robust host of palladium for heterogeneous catalysis: Suzuki reaction and the p-nitrophenol reduction.

In this study, the metal-organic framework ZIF-8 has been successfully planted on the surface of chitosan microspheres (CS/PDA@ZIF-8) using polydopamine as connecting material for the first time, which avoids the use of expensive, non-renewable, and non-biodegradable polystyrene microspheres commonly used as templates to prepare core-shell structures. Moreover, the metal-organic framework ZIF-8 was prepared specially by three different methods and all characterized by SEM, TEM, and BET, and the ZIF-8 shell prepared at room temperature presents a regular morphology, uniform size, large specific surface area (353.1 m2/g) than the shells prepared by the other methods including. The CS/PDA@ZIF-825@Pd with high catalytic activity and high stability was especially prepared by encapsulating Pd nanoparticles into the pores of CS/PDA@ZIF-825. Notably, the fabricated catalyst performed well in an array of reactions, for example the Kapp value of the p-nitrophenol reduction reaction reached 0.0426 s-1, and the TOF of the Suzuki coupling reaction reached 128 h-1. In addition, the ZIF-67, UiO-66, UiO-66-NH2, HKUST-1, and NH2-MIL-53(Al) were also grown on chitosan microcapsules successively to prepare the core-shell microspheres, which prove the universal applicability of this strategy. And beyond that, the introduction of chitosan microspheres endows the material with biodegradable properties and excellent recycling properties.

Immobilizing of palladium on melamine functionalized magnetic chitosan beads: A versatile catalyst for p-nitrophenol reduction and Suzuki reaction in aqueous medium.

In this study, an environmental-friendly palladium catalyst with high efficiency, magnetic, recoverability, reusability, and excellent stability was prepared and thoroughly characterized by the Fourier transform infrared spectroscopy (FT-IR), Scanning electron microscopy (SEM), X-ray diffraction (XRD), Elemental mapping, Thermogravimetric analysis (TGA) and Energy-dispersive X-ray spectroscopy (EDX). Results demonstrates that melamine provides a coordination point on the surface of chitosan microspheres, which provides a platform for the uniform distribution of palladium (II) and combines with palladium (II) firmly to avoid unnecessary leaching of nanoparticles. Besides, Fe3O4/CS-Me@Pd microcapsules exhibited high catalytic performance in reducing p-NP in water at room temperature (150-300 s). This composite was also effective in the Suzuki-Miyaura coupling reaction under mild conditions with high catalytic performance (TON = 3.8 × 104, TOF = 7.6 × 104). Reproducibility experiments also showed that Fe3O4/CS-Me@Pd microcapsules have high recovery efficiency and can work at least six times during these two catalytic reactions. The hot filtration test indicated that the catalyst has heterogeneous nature.

Ruthenium-catalyzed coupling of α-carbonyl phosphoniums with sulfoxonium ylides via C-H activation/Wittig reaction sequences.

A Ru(ii)-catalyzed coupling of various α-carbonyl phosphoniums with sulfoxonium ylides has been realized for the facile synthesis of 1-naphthols in good to excellent yields. This oxidant-free transformation proceeds through Ru-catalyzed C-H activation of phosphoniums, Ru-carbene insertion, and intramolecular Wittig reaction processes.

Empowering alcohols as carbonyl surrogates for Grignard-type reactions.

The Grignard reaction is a fundamental tool for constructing C-C bonds. Although it is widely used in synthetic chemistry, it is normally applied in early stage functionalizations owing to poor functional group tolerance and less availability of carbonyls at late stages of molecular modifications. Herein, we report a Grignard-type reaction with alcohols as carbonyl surrogates by using a ruthenium(II) PNP-pincer complex as catalyst. This transformation proceeds via a carbonyl intermediate generated in situ from the dehydrogenation of alcohols, which is followed by a Grignard-type reaction with a hydrazone carbanion to form a C-C bond. The reaction conditions are mild and can tolerate a broad range of substrates. Moreover, no oxidant is involved during the entire transformation, with only H2 and N2 being generated as byproducts. This reaction opens up a new avenue for Grignard-type reactions by enabling the use of naturally abundant alcohols as starting materials without the need for pre-synthesizing carbonyls.

Ruthenium-catalyzed α-carbonyl sulfoxonium ylide annulations with aryl substituted pyrazoles via C-H/N-H bond functionalizations.

An efficient method for the construction of various pyrazolo[5,1-a]isoquinolines has been achieved via Ru(ii)-catalyzed α-carbonyl sulfoxonium ylide annulations with aryl substituted pyrazoles. This oxidant-free transformation occurred through pyrazole-directed C-H activation, Ru-carbene insertion, and acid-promoted carbonyl condensation processes, enabling dual C-C and C-N bond formation. A broad substrate scope with respect to both coupling components worked efficiently with high yields.

Light-Driven Metal-Free Direct Deoxygenation of Alcohols under Mild Conditions.

Hydroxyl is widely found in organic molecules as functional group and its deprivation plays an inevitable role in organic synthesis. However, the direct cleavage of Csp3-O bond in alcohols with high selectivity and efficiency, especially without the assistance of metal catalyst, has been a formidable challenge because of its strong bond dissociation energy and unfavorable thermodynamics. Herein, an efficient metal-free strategy that enables direct deoxygenation of alcohols has been developed for the first time, with hydrazine as the reductant induced by light. This protocol features mild reaction conditions, excellent functional group tolerance, and abundant and easily available starting materials, rendering selective deoxygenation of a variety of 1° and 2° alcohols, vicinal diols, and ß-1 and even ß-O-4 models of natural wood lignin. This strategy is also highlighted by its "traceless" and non-toxic by-products N2 and H2, as readily escapable gases. Mechanistic studies demonstrated dimethyl sulfide being a key intermediate in this transformation.

Magnetically recyclable Ag/TiO2 co-decorated magnetic silica composite for photodegradation of dibutyl phthalate with fluorescent lamps.

In recent years, industrial contaminants and especially organic pollutions have been threatening both environmental safety and human health. Particularly, dibutyl phthalate (DBP) has been considered as one of the major hazardous contaminants due to its widespread production and ecological toxicities. Consequently, reliable methods toward the efficient and environmentally benign degradation of DBP in wastewater would be very desirable. To this end, a novel magnetically separable porous TiO2/Ag composite photocatalyst with magnetic Fe3O4 particles as the core was developed and successfully introduced to the photocatalytic degradation of DBP under visible irradiation with a fluorescent lamp. The presented work describes the grafting of Ag co-doped TiO2 composite on the silica-modified porous Fe3O4 magnetic particles with a simple and inexpensive chemical co-precipitation method. Through the investigation of the influencing factors including photocatalyst dosage, initial concentration of DBP, solution pH, and H2O2 content, we found that the degradation efficiency could reach 74%. The photodegradation recovery experiment showed that the degradation efficiency of this photocatalyst remained almost the same after five times of reuse. In addition, a plausible degradation process was also proposed involving the attack of active hydroxyl radicals generated from this photocatalysis system and production of the corresponding intermediates of butyl phthalate, diethyl phthalate, dipropyl phthalate, methyl benzoate, and benzoic acid.

Palladium-Catalyzed Formal Hydroalkylation of Aryl-Substituted Alkynes with Hydrazones.

We have developed an unprecedented Pd-catalyzed formal hydroalkylation of alkynes with hydrazones, which are generated in situ from naturally abundant aldehydes, as both alkylation reagents and hydrogen donors. The hydroalkylation proceeds with high regio- and stereoselectivity to form (Z)-alkenes, which are more difficult to generate compared to (E)-alkenes. The reaction is compatible with a wide range of functional groups, including hydroxy, ester, ketone, nitrile, boronic ester, amine, and halide groups. Furthermore, late-stage modifications of natural products and pharmaceutical derivatives exemplify its unique chemoselectivity, regioselectivity, and synthetic applicability. Mechanistic studies indicate the possible involvement of Pd-hydride intermediates.

Palladium-catalyzed hydroalkylation of methylenecyclopropanes with simple hydrazones.

A palladium-catalyzed hydroalkylation reaction of methylenecyclopropanes via highly selective C-C σ-bond scission was achieved under mild conditions, in which simple hydrazones served as carbanion equivalents. This method featured good functional group compatibility, affording high yields of C-alkylated terminal alkenes.

Functionalized magnetic mesoporous silica/poly(m-aminothiophenol) nanocomposite for Hg(II) rapid uptake and high catalytic activity of spent Hg(II) adsorbent.

Currently, magnetic mesoporous silica nanospheres have been employed widely as adsorbents due to their large surface area and easy recovery. Herein, the functionalized magnetic mesoporous silica/organic polymers nanocomposite (MMSP) was fabricated by the grafted poly(m-aminothiophenol) embedded the aminated magnetic mesoporous silica nanocomposite based on Fe3O4 magnetic core, which was shelled by mesoporous silica and further modified by (3-aminopropyl) triethoxysilane. The adsorption properties of as-developed MMSP were systematically explored by altering the experimental parameters. The results indicated that the adsorption capacity and removal percentage of the MMSP could reach 243.83 mg/g and 97.53% within only 10 min at pH 4.0, and the coexisting ions had no significant effect on the selective Hg(II) ions removal from aqueous solutions, meanwhile, the adsorbent recovered by a magnet still exhibited good adsorption performance after recycled 5 times. In addition, by analyzing experimental data, the adsorption process of Hg(II) ions belonged to spontaneous exothermic adsorption, and the possible adsorption mechanisms were proposed based on the pseudo-second-order model and Langmuir model. After adsorption study, the waste material adsorbed Hg(II) was developed as an efficient catalyst for transformation of phenylacetylene to acetophenone with yield of 97.06%. In this study, we designed an efficient and selective material for Hg(II) ions remove and provided a treatment of the post-adsorbed mercury adsorbent by converting the waste into an excellent catalyst, which reduced the economic and environmental impact from conventional adsorption techniques.

New liquid crystal polycarbonate micelles for intracellular delivery of anticancer drugs.

To construct pH/temperature dual sensitive micelles as novel drug delivery carriers, the synthesis of two diblock copolymers mPEG113-PMCC9-(PMCC-DBO)27 and mPEG43-PMCC25-(PMCC-DHO)15 based on mPEG and polycarbonate modified by acid and liquid crystal groups is described. In aqueous solution, mPEG113-PMCC9-(PMCC-DBO)27 and mPEG43-PMCC25-(PMCC-DHO)15 could self-assemble to form nanospheres and vesicles at very low critical micelle concentration, respectively. Both nanospheres and vesicles were less than 100 nm in diameter and demonstrated high loading capacity of doxorubicin (DOX) through ionic interaction between the free carboxyl groups in PMCC segments and the amine groups in DOX. In vitro release studies indicated that the two copolymer micelles were capable of pH/temperature-triggered release of doxorubicin and without a significant initial burst release. Furthermore, MTT assays showed that the blank copolymer micelles were nontoxic, while the drug-loaded micelles exhibited potent cytotoxic activity towards HeLa cells. These pH/temperature responsive copolymer micelles provided a new strategy for constructing stimuli-responsive drug delivery carriers in chemotherapy.

Straightforward Synthesis of Bifunctional Phosphorus Phenols via Phosphination of In Situ Generated o-Quinone Methides.

An efficient and practical approach towards bifunctional phosphorus phenols has been developed through a reaction of diphenylphosphine oxide and the o-quinone methides in situ generated from 2-tosylalkyl phenols under basic conditions. This protocol features simple experimental procedures under mild conditions and is easily scaled up. With this method, a variety of diarylmethyl phosphine oxides can be produced with up to 92% yield.

Synthesis, Self-Assembly, and Drug-Release Properties of New Amphipathic Liquid Crystal Polycarbonates.

New amphiphilic liquid crystal (LC) polycarbonate block copolymers containing side-chain cholesteryl units were synthesized. Their structure, thermal stability, and LC phase behavior were characterized with Fourier transform infrared (FT-IR) spectrum, ¹H NMR, gel permeation chromatographic (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), polarizing optical microscope (POM), and XRD methods. The results demonstrated that the LC copolymers showed a double molecular arrangement of a smectic A phase at room temperature. With the elevating of LC unit content in such LC copolymers, the corresponding properties including decomposition temperature (Td), glass temperature (Tg), and isotropic temperature (Ti) increased. The LC copolymers showed pH-responsive self-assembly behavior under the weakly acidic condition, and with more side-chain LC units, the self-assembly process was faster, and the formed particle size was smaller. It indicated that the self-assembly driving force was derived from the orientational ability of LC. The particle size and morphologies of self-assembled microspheres loaded with doxorubicin (DOX), together with drug release tracking, were evaluated by dynamic light scattering (DLS), SEM, and UV-vis spectroscopy. The results showed that DOX could be quickly released in a weakly acidic environment due to the pH response of the self-assembled microspheres. This would offer a new strategy for drug delivery in clinic applications.

Synthesis and Self-Assembled Behavior of pH-Responsive Chiral Liquid Crystal Amphiphilic Copolymers Based on Diosgenyl-Functionalized Aliphatic Polycarbonate.

The morphological control of polymer micellar aggregates is an important issue in applications such as nanomedicine and material science. Stimuli responsive soft materials have attracted significant attention for their well-controlled morphologies. However, despite extensive studies, it is still a challenge to prepare nanoscale assemblies with responsive behaviors. Herein, a new chiral liquid crystal (LC) aliphatic polycarbonate with side chain bearing diosgenyl mesogen, named mPEG43-PMCC25-P(MCC-DHO)15, was synthesized through the ring-opening polymerization and coupling reaction. The self-assembled behavior of the LC copolymer was explored. In aqueous solution, the functionalized copolymer could self-organize into different nanostructures with changing pH value, such as nanospheres and nanofibers. This would offer new possibilities in the design of nanostructured organic materials.