Complementary specificity of unspecific peroxygenases enables access to diverse products from terpene oxygenation

TY - JOUR

T1 - Complementary specificity of unspecific peroxygenases enables access to diverse products from terpene oxygenation

AU - Melling, Benjamin

AU - Mielke, Tamara

AU - Whitwood, Adrian C.

AU - O'Riordan, Timothy J.C.

AU - Mulholland, Nicholas

AU - Cartwright, Jared

AU - Unsworth, William P.

AU - Grogan, Gideon

N1 - Funding Information: We thank the UK Engineering and Physical Sciences Research Council ( EPSRC ) and Syngenta for the award of a studentship to B.M. (project 2602946 ) and the Industrial Affiliates of the Center of Excellence for Biotransformations, Bioprocessing, and Biomanufacturing ( CoEBio3 ) for the award of a studentship to T.M. Publisher Copyright: © 2023 The Authors

PY - 2024/2/15

Y1 - 2024/2/15

N2 - Unspecific peroxygenases (UPOs) have emerged as attractive biocatalysts for selective oxygenations because, unlike cytochromes P450, they can be employed as easy-to-use lyophilized powders and depend only upon hydrogen peroxide as the external oxidant. The application of UPOs to a range of synthetic challenges relies on the characterization of activity and specificity of complementary enzymes. Here, we show that two UPOs, artUPO and rAaeUPO-PaDa-I-H, which are representative members of the “short” family I and “long” family II UPOs, display complementary activity in a series of scalable, preparative biotransformations of a diverse array of terpenes. The UPOs were also applied to the biotransformation of chrysanthemic-acid-derived fragments relevant in the agrichemical industry, culminating in the highly diastereoselective and enantioselective oxidation of a racemic synthetic pyrethroid derivative via kinetic resolution.

AB - Unspecific peroxygenases (UPOs) have emerged as attractive biocatalysts for selective oxygenations because, unlike cytochromes P450, they can be employed as easy-to-use lyophilized powders and depend only upon hydrogen peroxide as the external oxidant. The application of UPOs to a range of synthetic challenges relies on the characterization of activity and specificity of complementary enzymes. Here, we show that two UPOs, artUPO and rAaeUPO-PaDa-I-H, which are representative members of the “short” family I and “long” family II UPOs, display complementary activity in a series of scalable, preparative biotransformations of a diverse array of terpenes. The UPOs were also applied to the biotransformation of chrysanthemic-acid-derived fragments relevant in the agrichemical industry, culminating in the highly diastereoselective and enantioselective oxidation of a racemic synthetic pyrethroid derivative via kinetic resolution.

KW - cytochromes P450

KW - C–H activation

KW - oxygenation

KW - SDG9: Industry, innovation, and infrastructure

KW - terpenes

KW - unspecific peroxygenases

KW - UPOs

UR - http://www.scopus.com/inward/record.url?scp=85187268764&partnerID=8YFLogxK

U2 - 10.1016/j.checat.2023.100889

DO - 10.1016/j.checat.2023.100889

M3 - Article

AN - SCOPUS:85187268764

SN - 2667-1093

VL - 4

JO - CHEM: Catalysis

JF - CHEM: Catalysis

IS - 2

M1 - 100889

ER -