Peroxygenase-Enabled Reductive Kinetic Resolution for the Enantioenrichment of Organoperoxides.

Autor: Shen Q; Key Laboratory of Engineering Biology for Low-carbon Manufacturing Tianjin Institute of Industrial Biotechnology, Chinese Academy of Sciences, 32 West 7th Avenue, Tianjin, 300308, China.; School of Chemical Engineering and Technology, Xi'an Jiaotong University, Xi'an, 710049, China., Yan J; Key Laboratory of Engineering Biology for Low-carbon Manufacturing Tianjin Institute of Industrial Biotechnology, Chinese Academy of Sciences, 32 West 7th Avenue, Tianjin, 300308, China., Han Y; Key Laboratory of Engineering Biology for Low-carbon Manufacturing Tianjin Institute of Industrial Biotechnology, Chinese Academy of Sciences, 32 West 7th Avenue, Tianjin, 300308, China., Zhang Z; School of Chemical Engineering and Technology, Xi'an Jiaotong University, Xi'an, 710049, China., Li H; Key Laboratory of Engineering Biology for Low-carbon Manufacturing Tianjin Institute of Industrial Biotechnology, Chinese Academy of Sciences, 32 West 7th Avenue, Tianjin, 300308, China., Kong D; School of Pharmacy, Hainan Medical University, Haikou, 571199, Hainan, China., Shi J; College of Chemistry and Chemical Engineering, Hainan Normal University, Haikou, 571158, Hainan, China., Cui C; Key Laboratory of Engineering Biology for Low-carbon Manufacturing Tianjin Institute of Industrial Biotechnology, Chinese Academy of Sciences, 32 West 7th Avenue, Tianjin, 300308, China., Zhang W; Key Laboratory of Engineering Biology for Low-carbon Manufacturing Tianjin Institute of Industrial Biotechnology, Chinese Academy of Sciences, 32 West 7th Avenue, Tianjin, 300308, China.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 May 21; Vol. 63 (21), pp. e202401590. Date of Electronic Publication: 2024 Apr 03.
DOI: 10.1002/anie.202401590
Abstrakt: Enantiomerically pure organoperoxides serve as valuable precursors in organic transformations. Herein, we present the first examples of unspecific peroxygenase catalyzed kinetic resolution of racemic organoperoxides through asymmetric reduction. Through meticulous investigation of the reaction conditions, it is shown that the unspecific peroxygenase from Agrocybe aegerita (AaeUPO) exhibits robust catalytic activity in the kinetic resolution reactions of the model substrate with turnover numbers up to 60000 and turnover frequency of 5.6 s -1 . Various aralkyl organoperoxides were successfully resolved by AaeUPO, achieving excellent enantioselectivities (e.g., up to 99 % ee for the (S)-organoperoxide products). Additionally, we screened commercial peroxygenase variants to obtain the organoperoxides with complementary chirality, with one mutant yielding the (R)-products. While unspecific peroxygenases have been extensively demonstrated as a powerful oxidative catalysts, this study highlights their usefulness in catalyzing the reduction of organoperoxides and providing versatile chiral synthons.
(© 2024 Wiley-VCH GmbH.)
Databáze: MEDLINE