RESUMEN
An approach for the mild synthesis of selenoesters starting from selenoalkynes through an acid-catalyzed, redox-neutral oxyarylation reaction is reported. Brønsted acid activation of a selenoalkyne leads to a selenium-stabilized vinyl cation, which is captured by an aryl sulfoxide and undergoes sigmatropic rearrangement to deliver the final α-arylated selenoester product. Computational studies have been carried out to elucidate the nature of the Se-stabilized carbocation.
RESUMEN
A novel ynamide preactivation strategy enables the use of otherwise incompatible reagents and allows preparation of α,ß-disubstituted enamides with high regio- and stereoselectivity. Mechanistic analysis reveals the intermediacy of a triflate-bound intermediate as a solution-stable, effective keteniminium reservoir, whilst still allowing subsequent addition of organometallic reagents.