Direct Synthesis of β-Amino Aldehydes from Linear Allylic Esters Using O2 as the Sole Oxidant.

A tandem isomerization-anti-Markovnikov oxidation of linear allylic imidic esters is developed using bis(benzonitrile)palladium chloride as the catalyst and O2 as the sole oxidant, regiospecifically giving β-amino aldehydes as the product. tert-Butyl nitrite works as a simple, and the only, redox cocatalyst. tBuOH proves to be a crucial solvent for achieving excellent yield and specificity toward anti-Markovnikov aldehyde products.