Mechanism Behind the Programmed Biosynthesis of Heterotrimeric Fungal Depside Thielavin A

Overview

The polyketide synthase ThiA that forms the heterotrimeric fungal depside thielavin A (1) has been identified and characterized. The thioesterase (TE) domain of ThiA was found to perform two consecutive esterification reactions as well as subsequent hydrolysis, and a plausible reaction mechanism for the TE-catalyzed reactions has been proposed. Furthermore, this study provides insights into how ThiA selectivity yields the heterotrimeric product.