TEMPO-Mediated Dehydrogenative Hydroxyfluoroalkylation of Arylamines with Polyfluorinated Alcohols.

An efficient 2,2,6,6-tetramethylpiperidinooxy (TEMPO)-mediated hydroxyfluoroalkylation of arylamines with polyfluorinated alcohols via a radical-triggered C(sp2)-H/C(sp3)-H dehydrogenative cross-coupling process was developed. This transformation features simple operation, high atom economy, broad substrate compatibility, and excellent regioselectivity, leading to a series of hydroxyfluoroalkylated arylamine derivatives. Importantly, these synthetic products were further used to evaluate the antitumor activity in cancer cell lines by Cell Counting Kit-8 assay and the outcomes indicated that some compounds show a potent antiproliferative effect.

Peroxygenase-Enabled Reductive Kinetic Resolution for the Enantioenrichment of Organoperoxides.

Enantiomerically pure organoperoxides serve as valuable precursors in organic transformations. Herein, we present the first examples of unspecific peroxygenase catalyzed kinetic resolution of racemic organoperoxides through asymmetric reduction. Through meticulous investigation of the reaction conditions, it is shown that the unspecific peroxygenase from Agrocybe aegerita (AaeUPO) exhibits robust catalytic activity in the kinetic resolution reactions of the model substrate with turnover numbers up to 60000 and turnover frequency of 5.6 s-1. Various aralkyl organoperoxides were successfully resolved by AaeUPO, achieving excellent enantioselectivities (e.g., up to 99 % ee for the (S)-organoperoxide products). Additionally, we screened commercial peroxygenase variants to obtain the organoperoxides with complementary chirality, with one mutant yielding the (R)-products. While unspecific peroxygenases have been extensively demonstrated as a powerful oxidative catalysts, this study highlights their usefulness in catalyzing the reduction of organoperoxides and providing versatile chiral synthons.

Green synthesis and anti-tumor efficacy via inducing pyroptosis of novel 1H-benzo[e]indole-2(3H)-one spirocyclic derivatives.

Pyroptosis induction is anticipated to be a new approach to developing anti-tumor medications. A novel class of spirocyclic compounds was designed by hybridization of 1H-Benzo[e]indole-2(3H)-one with 1,4-dihydroquinoline and synthesized through a new green "one-pot" synthesis method using 10 wt% SDS/H2O as a solvent to screen novel tumor cell pyroptosis inducers. The anti-tumor activity of all compounds in vitro was determined by the MTT method, and a fraction of the compounds showed good cell growth inhibitory activity. The quantitative structure-activity relationship models of the compounds were established by artificial intelligence random forest algorithm (R2 = 0.9656 and 0.9747). The ideal compound A9 could, in a concentration-dependent manner, prevent ovarian cancer cells from forming colonies, migrating, and invading. Furthermore, A9 could significantly induce pyroptosis and upregulate the expression of pyroptosis-related proteins GSDME-N, in addition to inducing apoptosis and mediating the expression of apoptosis-related proteins in ovarian cancer cells. A9 (5 mg/kg) significantly reduced tumor volume and weight of ovarian cancer in vivo, decreased caspase-3 expression in tumor tissue, and induced the production of GSDME-N. This study provides a green and efficient atom-economic synthesis method for 1H-Benzo[e]indole-2(3H)-one spirocyclic derivatives and a promising pyroptosis inducer with anti-tumor activity.

KBrO3-Promoted Cross-Dehydrogenative Coupling Reaction: An Odorless Regioselective Sulfenylation of Imidazoheterocycles in Water.

A regioselective metal-free sulfenylation of imidazoheterocycles with heterocyclic thiols or thiones has been achieved using a cross-dehydrogenative coupling method in water. In addition, the procedure has several advantages including green solvents, free of foul-smelling sulfur sources, and mild conditions, thus providing considerable application potential in the pharmaceutical industry.

A novel methodology for the efficient synthesis of 3-monohalooxindoles by acidolysis of 3-phosphate-substituted oxindoles with haloid acids.

A novel method for the synthesis of 3-monohalooxindoles by acidolysis of isatin-derived 3-phosphate-substituted oxindoles with haloid acids was developed. This synthetic strategy involved the preparation of 3-phosphate-substituted oxindole intermediates and SN1 reactions with haloid acids. This new procedure features mild reaction conditions, simple operation, good yield, readily available and inexpensive starting materials, and gram-scalability.

KIO3-catalyzed cross dehydrogenative coupling reaction: sulfenylation of phenol and arylamine derivatives in water at room temperature.

A metal-free direct sulfenylation of phenol and arylamine derivatives with various heterocyclic thiols and thiones using a cross dehydrogenative coupling protocol in water at room temperature has been developed. In addition, this chemical method has several advantages including odorless sulfur sources, good functional group tolerance, green solvent, and mild conditions, making it more environmentally friendly.

Preparation of biodiesel oil-in-water nanoemulsions by mixed surfactants for bifenthrin formulation.

Although several approaches have been reported on the development of nanoemulsions over the last few years, studies on the formation of biodiesel nanoemulsions for bifenthrin formulation by the low-energy phase inversion composition (PIC) method are still scarce. Herein, the preparation of oil-in-water (O/W) nanoemulsions suitable for pesticide application has been achieved in biodiesel by dissolving a bifenthrin/mixture of a non-ionic surfactant (NP-6) and an anionic surfactant (ABSCa)/water system by the PIC method. The mechanism of the formation of bifenthrin nanoemulsions by dripping the water phase into the oil-surfactant phase was exemplified via the pseudo-ternary phase diagram. The effects of the mass ratio of NP-6 and ABSCa, mROS, stirring rate, the addition rate of water and the emulsification temperature on the mean droplet size of the nanoemulsion were investigated by dynamic light scattering (DLS). In addition, the interfacial tension and the contact angle of bifenthrin nanoemulsions for the spraying application were investigated. The insecticidal activity of bifenthrin nanoemulsions against cabbage maggots was further studied. Moreover, the emulsion stability of the bifenthrin nanoemulsions against Ostwald ripening behavior was evaluated, and the long-term stability of the bifenthrin formulation was studied by the HPLC method to assess the shelf life of the pesticide formulation. Experimental results showed that the optimum emulsification conditions for the mass ratio of NP-6 and ABSCa, mROS, stirring rate, the addition rate of water and the emulsification temperature were respectively 5/5, 1.4, 8000 rpm, 0.7 mL min-1 and 25 °C. The bifenthrin nanoemulsion with low interfacial tension and contact angle, easy adsorption on plant leaf surfaces and good shelf life has great potential for use as a pesticide formulation.

6-Amino-3-methyl-4-(3-nitro-phen-yl)-1-phenyl-1H,4H-pyrano[2,3-c]pyrazole-5-carbonitrile.

The title compound, C(20)H(15)N(5)O(3), was synthesized by the one-pot reaction of a four-component reaction protocol in aqueous medium. The pyrano[2,3-c]pyrazole system is essentially planar, with a maximum deviation of 0.026 (2) Å. The 3-nitro-phenyl and phenyl rings make dihedral angles of 81.11 (5) and 13.36 (1)°, respectively, with the mean plane of the pyrano[2,3-c]pyrazole ring. The crystal structure is stabilized by N-H⋯N hydrogen bonds, which form infinite chain propagating along the c axis and by N-H⋯O hydrogen bonds, which form infinite chains propagating along the a axis. There are also N-O⋯N-C dipole-dipole inter-actions along the a axis with an O⋯N distance of 3.061 (3) Å, which is shorter than that of the N-H⋯O hydrogen bond [3.196 (3) Å].

9-(1,1-Dimethyl-3-oxobut-yl)adenine.

The title compound, C(11)H(15)N(5)O, crystallizes with two independent mol-ecules in the asymmetric unit, both of which contain essentially planar imidazole and pyrimidine rings [maximum deviations = 0.002 (2) and 0.026 (2) Å, respectively, for the first mol-ecule, and 0.001 (2) and 0.025 (2) Šfor the second]; the dihedral angles between the rings are 2.1 (2) and 1.7 (2)° in the two mol-ecules. The crystal structure is stabilized by inter-molecular N-H⋯N hydrogen bonds, defining chains along a, which are further linked by weak inter-molecular π-π contacts [centroid centroid distance = 3.7989 (16) Å] into planes parallel to (01).