Divergent Oxidation Reactions of E- and Z-Allylic Primary Alcohols by an Unspecific Peroxygenase

TY - JOUR

T1 - Divergent Oxidation Reactions of E- and Z-Allylic Primary Alcohols by an Unspecific Peroxygenase

AU - Grogan, Gideon James

AU - Li, Jason

AU - Duran, Cristina

AU - Pogranyi, Balazs

AU - Cornish, Katy

AU - Osuna, Silvia

AU - Unsworth, William Paul

PY - 2024/12/10

Y1 - 2024/12/10

N2 - 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 (>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.

AB - 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 (>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.

U2 - 10.1002/anie.202422241

DO - 10.1002/anie.202422241

M3 - Article

SN - 1433-7851

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

M1 - e202422241

ER -