A direct visible light-induced generation of a hybrid aryl Pd-radical species from aryl iodide and Pd(0) is reported to enable an unprecedented (for hybrid Pd-radical species) hydrogen atom-transfer event. This approach allowed for efficient desaturation of readily available silyl ethers into synthetically valuable silyl enols. Moreover, this oxidation reaction proceeds at room temperature without the aid of exogenous photosensitizers or oxidants.
Son of sevenless homologue 1 (SOS1) is a guanine nucleotide exchange factor that catalyzes the exchange of GDP for GTP on RAS. In its active form, GTP-bound RAS is responsible for numerous critical cellular processes. Aberrant RAS activity is involved in ∼30% of all human cancers; hence, SOS1 is an attractive therapeutic target for its role in modulating RAS activation. Here, we describe a new series of benzimidazole-derived SOS1 agonists. Using structure-guided design, we discovered small molecules that increase nucleotide exchange on RAS in vitro at submicromolar concentrations, bind to SOS1 with low double-digit nanomolar affinity, rapidly enhance cellular RAS-GTP levels, and invoke biphasic signaling changes in phosphorylation of ERK 1/2. These compounds represent the most potent series of SOS1 agonists reported to date.
The ability of algae to accumulate metals and reduce metal ions make them a superior contender for the biosynthesis of nanoparticles and hence they are called bio-nano factories as both the live and dead dried biomass are used for the synthesis of metallic nanoparticles. Microalgae, forming a substantial part of the planet’s biodiversity, are usually single-celled colony-forming or filamentous photosynthetic microorganisms, including several legal divisions like Chlorophyta, Charophyta, and Bacillariophyta. Whole cells of Plectonema boryanum (filamentous cyanobacteria) proved efficient in promoting the production of Au, Ag, and Pt nanoparticles. The cyanobacterial strains of Anabaena flos-aquae and Calothrix pulvinate were used to implement the biosynthesis of Au, Ag, and Pt nanoparticles. Once synthesized within the cells, the nanoparticles were released into the culture media where they formed stable colloids easing their recovery. Lyngbya majuscule and Chlorella vulgaris have been reported to be used as a cost-effective method for Ag nanoparticle synthesis. Dried edible algae (Spirulina platensis) was reported to be used for the extracellular synthesis of Au, Ag, and Au/Ag bimetallic nanoparticles. Synthesis of extracellular metal bio-nanoparticles using Sargassum wightii and Kappaphycus alvarezi has also been reported. Bioreduction of Au (III)-Au (0) using the biomass of brown alga, Fucus vesiculosus, and biosynthesis of Au nanoparticles using red algal (Chondrus crispus) and green algal (Spyrogira insignis) biomass have also been reported. Algae are relatively convenient to handle, less toxic, and less harmful to the environment; synthesis can be carried out at ambient temperature and pressure and in simple aqueous media at a normal pH value. Therefore, the study of algae-mediated biosynthesis of metallic nanoparticles can be taken toward a new branch, termed phyco-nanotechnology.
The efficient Pd-catalyzed double-fold C-H oxygenation of arenes into resorcinols using newly developed 2-pyrimidyldiisopropylsilyl (PyrDipSi) directing group is described. Its employment allows for a sequential introduction of OAc and OPiv groups in a one-pot manner to produce orthogonally protected resorcinol derivatives. PyrDipSi group is superior over the previously developed 2-pyridyldiisopropylsilyl (PyDipSi) group, as it is efficient for monooxygenation of ortho-substituted arenes. Notably, PyrDipSi group can be easily installed into arene molecule and can be easily removed or modified after the oxygenation reaction.
Two-fold unsymmetrical functionalization of arenes, which includes sequential halogenation/oxygenation reactions, has been developed. This transformation allows for a general and efficient synthesis of substituted meta-halophenols from simple aryl iodides. Importantly, the PyrDipSi (2-diisopropylsilylpyrimidine) group can be easily removed or efficiently converted into valuable functionalities.
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