Divergent Oxidation Reactions of <i>E</i>‐ and <i>Z</i>‐Allylic Primary Alcohols by an Unspecific Peroxygenase

Abstract Unspecific peroxygenases (UPOs) catalyze the selective oxygenation of organic substrates using only hydrogen peroxide as the external oxidant. The PaDa−I variant of the UPO from Agrocybe aegerita catalyses the oxidation of Z ‐ and E ‐allylic alcohols with complementary selectivity, giving epoxide and carboxylic acid/aldehyde products respectively. Both reactions can be performed on preparative scale with isolated yields up to 80 %, and the epoxidations proceed with excellent enantioselectivity (&gt;99 % ee ). The divergent reactions can also be used to transform E / Z mixtures of allylic alcohols, enabling both product series to be isolated from a single reaction. The utility of the epoxidation method is exemplified in the total synthesis of both enantiomers of the insect pheromone disparlure, including a highly enantioselective gram‐scale transformation. These reactions provide further evidence for the potential of UPOs as catalysts for the scalable preparation of important oxygenated intermediates.