Dendritic mesoporous nanoparticles for the detection, adsorption, and degradation of hazardous substances in the environment: State-of-the-art and future prospects.

Equipped with hierarchical pores and three-dimensional (3D) center-radial channels, dendritic mesoporous nanoparticles (DMNs) make their pore volumes extremely large, specific surface areas super-high, internal spaces especially accessible, and so on. Other entities (like organic moieties or nanoparticles) can be modified onto the interfaces or skeletons of DMNs, accomplishing their functionalization for desirable applications. This comprehensive review emphasizes on the design and construction of DMNs-based systems which serve as sensors, adsorbents and catalysts for the detection, adsorption, and degradation of hazardous substances, mainly including the construction procedures of brand-new DMNs-based materials and the involved hazardous substances (like industrial chemicals, chemical dyes, heavy metal ions, medicines, pesticides, and harmful gases). The sensitive, adsorptive, or catalytic performances of various DMNs have been compared; correspondingly, the reaction mechanisms have been revealed strictly. It is honestly anticipated that the profound discussion could offer scientists certain enlightenment to design novel DMNs-based systems towards the detection, adsorption, and degradation of hazardous substances, respectively or comprehensively.

Synthesis and Antifungal Activity of Derivatives of the Natural Product Griseofulvin against Phytopathogenic Fungi.

Natural products are important sources for the discovery of new pesticides. Chemical synthesis and structural modification can lead to pesticides. Despite abundant research in fungicide discovery for crop protection, there is an emerging need for the development of novel antifungal agrochemicals. Herein, 39 diversified griseofulvin derivatives were effectively synthesized from the natural product griseofulvin by diversity-oriented synthesis through the reactions of demethylation, ammonolysis, methylation, nitration, acylation, reduction, and chlorination. Among them, 31 derivatives were novel. All structures were characterized by 1H NMR, 13C NMR, and high-resolution mass spectrometry (HR-MS), and the antifungal activity was investigated against five phytopathogenic fungi. Compounds 5h and 5l had excellent activity against Botrytis cinerea (5h, IC50 = 17.29 ± 0.64 µg/mL) and Alternaria solani (5l, IC50 = 22.52 ± 0.79 µg/mL), respectively. Compound 9 exhibited the more promising activities against three target fungi, especially against Colletotrichum gloeosporioides (IC50 = 7.24 ± 0.66 µg/mL), which is obviously better than positive control hymexazol, thifluzamide, and parent compound griseofulvin. In addition, compound 10 showed significant and extensive activities against four target fungi Cytospora sp. (IC50 = 18.72 ± 0.35 µg/mL), C. gloeosporioides (IC50 = 31.39 ± 1.48 µg/mL), A. solani (IC50 = 40.82 ± 1.04 µg/mL), and Fusarium solani (IC50 = 36.81 ± 0.82 µg/mL). Unexpectedly, 11 and 12, the chlorinated products of compound 9, exhibited the most promising activity against C. gloeosporioides (IC50 = 4.48 ± 0.54 µg/mL for 11, 2.24 ± 0.76 µg/mL for 12). Furthermore, 12 showed remarkable activity against Cytospora sp. (IC50 = 5.85 ± 0.72 µg/mL). Additionally, in vivo antifungal activity against C. gloeosporioides, homology modeling, and docking analysis of 11, 12, and griseofulvin were conducted. All results indicated that 11 and 12 had potency as antifungal agents against C. gloeosporioides, and the modifications of the 2' and 4' positions of griseofulvin should be further explored for higher-activity lead compounds or potential agricultural fungicides.

One-Pot Synthesis of Unprotected 2-Acylpyrroles from 1,2,3-Triazoles and 2-Hydroxymethylallyl Carbonates.

An efficient, tandem one-pot approach to synthesize multisubstituted 2-acylpyrroles from readily prepared N-tosyl triazoles and 2-hydroxymethylallyl carbonates is reported. The reaction proceeds via Rh(II)-catalyzed O-H insertion, [3,3]-sigmatropic rearrangement, Pd(0)-catalyzed oxidative addition, intramolecular cyclization, DBU-promoted E1cB elimination, double bond isomerization, and aromatization, enabling the disconnection and formation of multiple bonds in one reactor. The approach represents a highly regioselective way to access di-, tri-, and tetra-substituted NH pyrroles with high efficiency.

Dual Rh(II)/Pd(0) Relay Catalysis Involving Sigmatropic Rearrangement Using N-Sulfonyl Triazoles and 2-Hydroxymethylallyl Carbonates.

Dual Rh(II)/Pd(0) relay catalysis of N-sulfonyl triazoles and 2-hydroxymethylallyl carbonates has been developed, which affords N-sulfonyl pyrrolidines in moderate to good yields with high diastereoselectivities. The reaction proceeds via a relay mechanism involving O-H insertion onto the α-imino Rh(II)-carbene, [3,3]-sigmatropic rearrangement, dipole formation through Pd(0)-catalyzed decarboxylation, and intramolecular N-allylation, leading to the formation of multiple bonds in a one-pot operation.

Syntheses of Benzo[c]Chromen-6-ones by Palladium Catalyzed C-H Bond Activation using Diazonium Salts.

An efficient palladium catalyzed C-H bond activation for the synthesis of benzo[c]chromen-6-ones using diazonium salts is described. In the presence of Pd(OAc)2, dppp, PivOH and K2CO3, the diazonium salt can be transformed into the product through a denitrogenation/C-H bond activation/cyclization sequence in acetonitrile. Altogether, nine structurally diverse substituted benzoLc]chromen-6-ones were prepared in excellent yields through two different methods.

A facile synthesis of (+/-)-heliannuol-D.

A facile synthesis of (+/-)-heliannuol-D 1, which serves as an allelopathic chemical in nature and a potential lead compound in the search for new herbicides, has been achieved in a linear 11 steps, together with its epimer. The synthesis commenced with 4-methoxy-3-methyl-acetophenone, through the Baeyer-Villiger reaction, lithiation and addition, epoxidation and intramolecular cyclization to give (+/-)-heliannuol-D (1) and its epimer (la) in 32.6% overall yield. Our synthetic approach is cost-effective; this will be helpful in applying this kind of compound for the development of a new generation of agrochemicals.

A facile and efficient synthesis of diaryl amines or ethers under microwave irradiation at presence of KF/Al2O3 without solvent and their anti-fungal biological activities against six phytopathogens.

A series of diaryl amines, ethers and thioethers were synthesized under microwave irradiation efficiently at presence of KF/Al2O3 in 83%-96% yields without any solvent. The salient characters of this method lie in short reaction time, high yields, general applicability to substrates and simple workup procedure. At the same time, their antifungal biological activities against six phytopathogen were evaluated. Most of the compounds (3b, 3c, 3g-o) are more potent than thiophannate-methyl against to Magnaporthe oryzae. This implies that diaryl amine or ether moiety may be helpful in finding a fungicide against Magnaporthe oryzae.

An improved synthesis of 1,2-diarylethanols under conventional heating and ultrasound irradiation.

A simple and efficient synthesis of 1,2-diarylethanols has been developed. The procedure involved the reaction between a variety of toluene derivatives and aryl aldehydes under conventional heating and ultrasound irradiation. This procedure possesses several advantages such as operational simplicity, high yield, safety and environment benignancy. Ultrasound was proved to be very helpful to the reaction, markedly improving the yield and the reaction rate.

3,4-Bis(4-meth-oxy-phen-yl)-2,5-dihydro-1H-pyrrole-2,5-dione.

In the title compound, C(18)H(15)NO(4), the benzene rings form quite different dihedral angles [16.07 (1) and 59.50 (1)°] with the central pyrrole ring, indicating a twisted mol-ecule. Conjugation is indicated between the five- and six-membered rings by the lengths of the C-C bonds which link them [1.462 (3) and 1.477 (3) Å]. The most prominent feature of the crystal packing is the formation of inversion dimers via eight-membered {⋯HNCO}(2) synthons.

2-(4-Methyl-phen-yl)-1-(phenyl-sulfon-yl)propan-2-ol.

The title compound, C(16)H(18)O(3)S, features a U-shape mol-ecular structure with a dihedral angle between the terminal benzene rings of 20.8 (1)°. An intra-molecular O-H⋯O hydrogen bond helps to stabilize the mol-ecular structure. Inter-molecular classical O-H⋯O and weak C-H⋯O hydrogen bonding is present in the crystal structure.