Deoxysugar Formation via 4',5'‐Dehydration on PKS Assembly Line in Nucleoside Antibiotic Biosynthesis

Z Zi‐Hui Chen (Key Laboratory of Glyco‐drug Research of Zhejiang Province School of Chemistry and Materials Science Hangzhou Institute for Advanced Study University of Chinese Academy of Sciences Hangzhou China) F Fei Wang W Weiyan Wang (Key Laboratory of Glyco‐drug Research of Zhejiang Province School of Chemistry and Materials Science Hangzhou Institute for Advanced Study University of Chinese Academy of Sciences Hangzhou China) T Tian‐Ci Zhang (Key Laboratory of Glyco‐drug Research of Zhejiang Province School of Chemistry and Materials Science Hangzhou Institute for Advanced Study University of Chinese Academy of Sciences Hangzhou China) Y Yi‐Lin Wang (Key Laboratory of Glyco‐drug Research of Zhejiang Province School of Chemistry and Materials Science Hangzhou Institute for Advanced Study University of Chinese Academy of Sciences Hangzhou China) W Wen‐He Zhang (State Key Laboratory of Chemical Biology Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences Shanghai China) J Jinyue Pu (Key Laboratory of Glyco‐drug Research of Zhejiang Province School of Chemistry and Materials Science Hangzhou Institute for Advanced Study University of Chinese Academy of Sciences Hangzhou China) A Aiai Sun (Key Laboratory of Glyco‐drug Research of Zhejiang Province School of Chemistry and Materials Science Hangzhou Institute for Advanced Study University of Chinese Academy of Sciences Hangzhou China) H Hai‐Xue Pan (Key Laboratory of Glyco‐drug Research of Zhejiang Province School of Chemistry and Materials Science Hangzhou Institute for Advanced Study University of Chinese Academy of Sciences Hangzhou China) G Gong‐Li Tang (Key Laboratory of Glyco‐drug Research of Zhejiang Province School of Chemistry and Materials Science Hangzhou Institute for Advanced Study University of Chinese Academy of Sciences Hangzhou China)

Abstract

ABSTRACT Amipurimycin is a peptidyl nucleoside antibiotic characterized by a C 9 high‐carbon sugar, with potent activity against the rice blast pathogen Pyricularia oryzae . The biosynthetic machinery of the C‐4' methylene group in its deoxy sugar has remained unknown. This study reveals that ApmL, a hypothetical protein in the DUF3500 family, functions as a 4′,5′‐dehydratase whose activity is strictly dependent on the PKS assembly line. Together with its partner reductase ApmM, they complete a two‐step C‐4′ deoxygenation process via dehydration‐reduction. We achieve the first in vitro reconstitution of this unique PKS‐coupled dehydration process and show direct interaction between ApmL and PKS proteins. Our findings establish ApmL as a new family of dehydratase and uncover a noncanonical deoxygenation strategy in nucleoside antibiotic biosynthesis.

Article Details

Volume / Issue Vol. 65, Issue 19
Published May 04, 2026
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (10)

Z

Zi‐Hui Chen

Key Laboratory of Glyco‐drug Research of Zhejiang Province School of Chemistry and Materials Science Hangzhou Institute for Advanced Study University of Chinese Academy of Sciences Hangzhou China

F

Fei Wang

W

Weiyan Wang

Key Laboratory of Glyco‐drug Research of Zhejiang Province School of Chemistry and Materials Science Hangzhou Institute for Advanced Study University of Chinese Academy of Sciences Hangzhou China

T

Tian‐Ci Zhang

Key Laboratory of Glyco‐drug Research of Zhejiang Province School of Chemistry and Materials Science Hangzhou Institute for Advanced Study University of Chinese Academy of Sciences Hangzhou China

Y

Yi‐Lin Wang

Key Laboratory of Glyco‐drug Research of Zhejiang Province School of Chemistry and Materials Science Hangzhou Institute for Advanced Study University of Chinese Academy of Sciences Hangzhou China

W

Wen‐He Zhang

State Key Laboratory of Chemical Biology Shanghai Institute of Organic Chemistry University of Chinese Academy of Sciences Chinese Academy of Sciences Shanghai China

J

Jinyue Pu

Key Laboratory of Glyco‐drug Research of Zhejiang Province School of Chemistry and Materials Science Hangzhou Institute for Advanced Study University of Chinese Academy of Sciences Hangzhou China

A

Aiai Sun

Key Laboratory of Glyco‐drug Research of Zhejiang Province School of Chemistry and Materials Science Hangzhou Institute for Advanced Study University of Chinese Academy of Sciences Hangzhou China

H

Hai‐Xue Pan

Key Laboratory of Glyco‐drug Research of Zhejiang Province School of Chemistry and Materials Science Hangzhou Institute for Advanced Study University of Chinese Academy of Sciences Hangzhou China

G

Gong‐Li Tang

Key Laboratory of Glyco‐drug Research of Zhejiang Province School of Chemistry and Materials Science Hangzhou Institute for Advanced Study University of Chinese Academy of Sciences Hangzhou China