A tandem isomerization--Markovnikov oxidation of linear allylic imidic esters is developed using bis(benzonitrile)palladium chloride as the catalyst and O as the sole oxidant, regiospecifically giving β-amino aldehydes as the product. -Butyl nitrite works as a simple, and the only, redox cocatalyst. BuOH proves to be a crucial solvent for achieving excellent yield and specificity toward -Markovnikov aldehyde products.
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