Dedicated to the memory of academician N. S. Zefirov.Abstract: Solvent-free protocols for palladium-catalyzed stannylation of aryl halides, Stille cross-coupling, and one-pot, twostep stannylation/Stille cross-coupling (SSC) are reported for the first time. (Het)aryl halides bearing acceptor, donor, as well as sterically demanding substituents are stannylated and/or coupled in high yields. The reactions are catalyzed by conventional palladium(II) acetate/PCy 3 [Pd(OAc) 2 /PCy 3 ] under air, using avail-
Fischer's approach towards the synthesis of aryl azides and triazinoles from diazonium salts and hydroxylammonium chloride (phenylhydraxylamine) was reinvestigated and optimized.
A systematic study of TKX‐50 and ABTOX synthesis using both Klapötke and Tselinskii modified procedures is described. The influence of temperature, moisture, acid amount and nature on the most critical synthesis step – diazidoglyoxime cyclization is shown. Experimental results show that presence of moisture in reaction mixture leads to product yield decreasing. The reaction temperature is another key parameter affecting product yield. High reaction temperature shows negative influence on the product yield in Klapötke method. In Tselinskii procedure the yield of product grows with the reaction temperature increasing. For Klapötke one‐pot method, combination of N‐methyl‐2‐pyrrolidone with 1,4‐dioxane is the best solvent, whereas Tselinskii one‐pot procedure gives high yield of product when combination of toluene with 0.5 equiv. of 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) is used. Using optimized conditions one‐pot five‐step synthesis of TKX‐50 starting from glyoxime is successfully performed and scaled up to 50 g.
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