Genome-Based Discovery of Enantiomeric Pentacyclic Sesterterpenes Catalyzed by Fungal Bifunctional Terpene Synthases
Lan Jiang, Xue Zhang, Yuya Sato, Guoliang Zhu, Atsushi Minami, Weiyan Zhang, Taro Ozaki, Bin Zhu, Zhixin Wang, Xinye Wang, Kangjie Lv, Jingyu Zhang, Yongheng Wang, Shu‐Shan Gao, Chengwei Liu, Tom Hsiang, Lixin Zhang, Hideaki Oikawa, Xueting Liu
Abstract
Genome-based discovery of two previously unreported fungal bifunctional terpene synthases (BFTSs) from phytopathogenic fungi are reported: FoFS catalyzing the formation of fusoxypenes A–C (1–3) and (−)-astellatene (4) and AtAS capable of synthesizing preaspterpenacid I (6). Interestingly, FoFS and AtAS catalyzed the formation of enantiomeric sesterterpenes with a 5–6–7–3–5 ring system. C22-oxidative modification of preaspterpenacid I by AtP450 was characterized as well. Plausible cyclization pathways of the fusoxypenes were illustrated by DFT calculations.