Serious unfavorable quantity division
A facile and efficient In(OTf)3- and BF3·OEt2-catalyzed direct transformation of 3-formylindoles with diazo esters has been developed for synthesizing diverse and functionalized indolyl acrylates. This one-pot protocol furnishes various (Z)-α-hydroxy-β-indolyl acrylates, (E)-β-(2-alkoxy-2-oxoethoxy)-α-indolyl acrylates, and (Z)-3-hydroxy-2-indolyl acrylates by a catalyst- and substituent-controlled, regio- and stereoselective cascade reaction. The protocol has several advantages, including low loading of the catalyst, mild reaction conditions, broad scope, and high functional group tolerance. The synthesized compounds can be further converted into diversely functionalized materials.FDAPT (2-formyl-5-(4'-N,N-dimethylaminophenyl)thiophene) is an efficient environment-sensitive fluorescent probe, which senses the alteration of its microenvironment with six different fluorescent parameters, namely, emission intensity, wavelength, fluorescence anisotropy, and corresponding three time-dependent parameters fluorescence lifetime, time-resolved emission spectrum, and anisotropy decay. In the present work, the nature of saccharide-induced dehydration of a F127 polymeric micelle is investigated in detail with FDAPT emission. Using a multiparametric fluorescence approach, it is observed that the saccharide molecules not only decrease the critical micellization temperature of the F127 solution but also strongly alter the physical properties inside the micellar structures. The local polarity and fluidity significantly decrease in the saccharide-induced micelle as compared to the normal F127 micelle. The probe solvation dynamics study reveals that the water content in the core as well as corona domain diminishes significantly in the saccharide-induced micelle as compared to the normal micelle. More precisely, dehydration occurs more in the core region than in the corona region. Also, the saccharide-induced dehydration alters the relative size of the core and corona regions. The extent of dehydration varies with different saccharide molecules. It is also found that the dehydration efficiency order is trisaccharide (raffinose) > disaccharide (sucrose) > monosaccharide (glucose and fructose).The development of efficient and stable catalysts for the oxygen reduction reaction (ORR) at low cost is crucial for realizing the large-scale application of metal-air batteries. Herein, we report an efficient ORR catalyst of bimetallic copper and cobalt fluoride heterojunctions, which are uniformly dispersed in nitrogen-fluorine-oxygen triply doped porous carbon nanofibers (PCNFs) that contain hierarchical macro-meso-micro pores. The composite catalyst materials are fabricated with a facile and green method of electrospinning with water as the solvent. By using poly(tetrafluoroethylene) as the pore inducer to anchor electropositive copper and cobalt salts in the electrospun hybrid nanofibers, bimetallic fluoride heterojunctions can be directly formed in PCNFs after calcination. The hierachical porous structures provide an effective way to transport matter, while the bimetallic fluorides expose abundant electroactive sites, both of which result in stable ORR activities with a high half-wave potential of 0.84 V. The study proposes a feasible strategy for the fabrication of nonprecious catalysts.A palladium-catalyzed tandem carbonylative lactonization and Diels-Alder cycloaddition reaction between aldehyde-tethered benzylhalides and alkenes has been developed. A range of alkenes and aldehyde-tethered benzylhalides bearing different substituents can be successfully transformed into the corresponding bridged polycyclic compounds in good yields. This strategy provides a unique approach to complex lactone-containing bridged polycyclic compounds.Heteroarene boronate esters constitute valuable intermediates in modern organic synthesis. As building blocks, they can be further applied to the synthesis of new materials, since they can be easily transformed into any other functional group. Efforts toward novel and efficient strategies for their preparation are clearly desirable. StemRegenin 1 Here, we have achieved the borylation of commercially available heteroarene halides under very mild conditions in an easy-to-use gel nanoreactor. Its use of visible light as the energy source at room temperature in photocatalyst-free and aerobic conditions makes this protocol very attractive. The gel network provides an adequate stabilizing microenvironment to support wide substrate scope, including furan, thiophene, selenophene, and pyrrole boronate esters.Compared with traditional chemotherapeutics, vascular disruption agents (VDAs) have the advantages of rapidly blocking the supply of nutrients and starving tumors to death. Although the VDAs are effective under certain scenarios, this treatment triggers angiogenesis in the later stage of therapy that frequently leads to tumor recurrence and treatment failure. Additionally, the nonspecific tumor targeting and considerable side effects also impede the clinical applications of VDAs. Here we develop a customized strategy that combines a VDA with an anti-angiogenic drug (AAD) using mesoporous silica nanoparticles (MSNs) coated with platelet membrane for the self-assembled tumor targeting accumulation. The tailor-made nanoparticles accumulate in tumor tissues through the targeted adhesion of platelet membrane surface to damaged vessel sites, resulting in significant vascular disruption and efficient anti-angiogenesis in animal models. This study demonstrates the promising potential of combining VDA and AAD in a single nanoplatform for tumor eradication.The initial energy in a reactive intermediate is derived from the transition state before the intermediate but can affect selectivity after the intermediate. In this way an observable selectivity can report on a prior, kinetically hidden mechanistic step. This new type of mechanistic probe is demonstrated here for the oxidation of 1-methylcyclobutanol by phthaloyl peroxide/Bu4N+Br-, and it supports a hypobromite chain mechanism in place of the previously proposed hydrogen atom transfer mechanism.Although the parent 2-pyrone is known to react with simple o-benzynes to produce naphthalene derivatives, there appear to be no examples of the successful reaction of coumarin, a benzo-annulated 2-pyrone analogue, with an aryne. We report such a process here using benzynes generated by the hexadehydro-Diels-Alder reaction to produce phenanthrene derivatives (i.e., benzo-annulated naphthalenes). Density functional theory computations were used to help understand the difference in reactivity between 2-pyrone and the slower trapping agent, coumarin. Finally, the reaction of o-benzyne itself [from o-(trimethylsilyl)phenyl triflate and CsF] with coumarin was shown to be viable, although slow.