Aldehyde-Selective Wacker-Type Oxidation of Unbiased Alkenes Enabled by a Nitrite Co-Catalyst.

Breaking the rules: Reversal of the high Markovnikov selectivity of Wacker‐type oxidations was accomplished using a nitrite co‐catalyst. Unbiased aliphatic alkenes can be oxidized with high yield and aldehyde selectivity, and several functional groups are tolerated. 18O‐labeling experiments indicate that the aldehydic O atom is derived from the nitrite salt. [ABSTRACT FROM AUTHOR]