A regioselective arylative cyclization of ortho functional diaryl acetylenes for the synthesis of selectively substituted diaryl pyridine and indene derivatives is accomplished through an electrophile driven alkyne polarization.
A regio- and stereoselective thiocyanate addition to ynones is achieved using KSCN in AcOH at 70 °C. The reaction is extendable to ynals, ynesulfones, ynoic acids and ynoates. Adducts from ynones were readily transformed into thiazine-2-thione derivatives under slightly modified reaction conditions. In contrast, thiocyanated adducts from ynamides underwent an in situ decyanative amido cyclization towards isothiazolones. None of these events needed any transition metal or catalyst, attaining a high synthetic value.
An anti-carbonickelative cyclization via reversible alkenylnickel E/Z isomerization of 2-azido phenyl propargyl alcohols with aryl boronic acids is achieved using Ni(acac) as the catalyst to access 2,3-diaryl quinolines. It represents a rare example of trapping the vinyl metal intermediate with a nitrogen center, a non-carbon center electrophile.
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