Platinum particles were prepared by reducing the hydrogen hexachloroplatinate extracted in organic solvents from an aqueous solution by these extractants:dioctadecyldimethylammonium chloride(DDAC), trioctylmethylammonium chloride(TMAC), and trioctylphosphine oxide(TOPO). The extraction ratio of platinum(IV) increased in chloroform, isobutyl methyl ketone, and cyclohexane with an increase in the concentrations of the extractants, and then approached a constant state. The extracts were reduced by formaldehyde or benzaldehyde in the presence of water and a base (sodium hydroxide or triethylamine) for several hours at 65 °C. The platinum particles obtained in chloroform and isobutyl methyl ketone were very stable; their diameters were 15–25 Å.
Precious metal particles of platinum and silver have been prepared by the reduction of metal salts dissolved in an aqueous solution of a copolymer of vinyl alcohol and N-vinylpyrrolidone with methanol. The stable platinum sols were obtained in the presence of poly(vinyl alcohol), poly(N-vinylpyrrolidone), and their copolymers, but their particle sizes hardly changed with the ratio of N-vinylpyrrolidone in the copolymer. On the other hand, colloidal stable silver sols were obtained only in the presence of a copolymer. Further, with an increase in the ratio of N-vinylpyrrolidone in the copolymer, the particle size of silver became small.
An efficient method for constructing carbocycles with all-carbon quaternary stereocenters has been developed on the basis of a stereoselective cyclization reaction of α,β-unsaturated lactones having an alkanenitrile side chain. Treatment of the substrate with lithium hexamethyldisilazide (LiHMDS) in the presence of triisopropylsilyl chloride (TIPSCl) led to the generation of the corresponding α-cyano carbanion species which readily underwent an intramolecular conjugate addition reaction. It was found that the combined use of trimethylsilyl trifluoromethanesulfonate (TMSOTf) and triethylamine is also effective for the cyclization reaction without using a strong base. Interestingly, different stereochemical outcomes were observed in the two cyclization methods
Brasilicardins, bacterial diterpenoid natural products that display highly potent immunosuppressive activity, are promising immunosuppressant drug candidates. Structurally, they can be described as hybrids of terpenoids, amino acids, and saccharides, and share a characteristic highly strained anti‐syn‐anti‐fused perhydrophenanthrene terpenoid scaffold (ABC‐ring system) with two quaternary asymmetric carbon atoms. A unified and stereoselective total synthesis of all four brasilicardins has been designed based on the strategic use of an intramolecular conjugate addition. The ABC‐ring system was initially constructed with high stereocontrol by novel intramolecular conjugate additions of Weinreb amides and in situ generated (Z)‐vinyl copper species. The late‐stage common intermediate was subjected to stereoselective installation of the amino acid component, followed by introduction of the saccharide unit via glycosylation to accomplish the total synthesis of brasilicardins A–D. Our synthesis offers opportunities to synthesize various brasilicardin analogues for biological and pharmacological investigations.
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