Completing the Biosynthesis of the Clinically Important Diterpenoid Andrographolide in <i>Andrographis Paniculata</i>

S Sifan Wang M Miaomiao Liang (State Key Laboratory of Bioactive Substance and Function of Natural Medicines, NHC Key Laboratory of Natural Products, CAMS Key Laboratory of Enzyme and Biocatalysis of Natural Drugs) W Weiqiang Chen (Department of Civil and Environmental Engineering and Rice Advanced Materials Institute, Ken Kennedy Institute, Rice University, 6100 Main Street) H Huihua Wan (State Key Laboratory for Quality Ensurance and Sustainable Use of Dao‐di Herbs Key Laboratory of Beijing for Identification and Safety Evaluation of Chinese Medicine Institute of Chinese Materia Medica China Academy of Chinese Medical Sciences Beijing 100700 China) X Xiangxiao Meng (State Key Laboratory for Quality Ensurance and Sustainable Use of Dao‐di Herbs Key Laboratory of Beijing for Identification and Safety Evaluation of Chinese Medicine Institute of Chinese Materia Medica China Academy of Chinese Medical Sciences Beijing 100700 China) X Xuewen Zhu (State Key Laboratory for Quality Ensurance and Sustainable Use of Dao‐di Herbs Key Laboratory of Beijing for Identification and Safety Evaluation of Chinese Medicine Institute of Chinese Materia Medica China Academy of Chinese Medical Sciences Beijing 100700 China) Y Yuhong Lu (State Key Laboratory of Bioactive Substance and Function of Natural Medicines NHC Key Laboratory of Biosynthesis of Natural Products CAMS Key Laboratory of Enzyme and Biocatalysis of Natural Drugs Institute of Materia Medica Chinese Academy of Medical Sciences and Peking Union Medical College Beijing 100050 China) Q Qi Shen (Department of Cancer Institute, Xuzhou Medical University) C Chunhong Jiang (State Key Laboratory of Innovative Natural Medicine and TCM Injections Jiangxi Qingfeng Pharmaceutical Co. Ltd. Ganzhou 341008 China) N Ning Xie S Shilin Chen (Center for AIE Research, College of Materials Science and Engineering) M Meirong Jia (State Key Laboratory of Bioactive Substance and Function of Natural Medicines, NHC Key Laboratory of Natural Products, CAMS Key Laboratory of Enzyme and Biocatalysis of Natural Drugs) W Wei Sun

Abstract

Abstract Andrographolide is a prominent labdane diterpenoid extracted from Andrographis paniculata with exceptional anti‐inflammatory properties. Commercial production of andrographolide relies exclusively on extraction from plant resources. Although the scaffold of andrographolide ent ‐copalol has previously been biosynthesized, further oxidative modifications remain elusive. In this study, by taking an integrated analysis of transcriptomes and metabolomes, we were able to identify four cytochrome P450 enzymes constituting the minimal set of andrographolide biosynthetic genes. Specifically, ApCYP71D587 catalyzes the conversion of ent ‐copalol to 19‐hydroxy‐ ent ‐copalol. Subsequently, ApCYP71BE50 mediates the formation of the lactone ring, ultimately yielding andrograpanin. Then ApCYP706U5 accomplishes the third step by mediating the C‐3 hydroxylation reaction, thereby allowing the formation of 14‐deoxyandrographolide. Ultimately, ApCYP72F1 completes the biosynthetic generation of andrographolide with C‐14 hydroxylation of the lactone and rearrangement of the olefin bond. In addition, co‐expression of the minimal gene set in N. benthamiana engineered to produce ent ‐copalol feasibly produces andrographolide, thus establishing an innovative metabolic engineering strategy to produce this medicine of historical importance, circumventing the need for plant extraction.

Article Details

Volume / Issue Vol. 64, Issue 31
Published July 28, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (13)

S

Sifan Wang

M

Miaomiao Liang

State Key Laboratory of Bioactive Substance and Function of Natural Medicines, NHC Key Laboratory of Natural Products, CAMS Key Laboratory of Enzyme and Biocatalysis of Natural Drugs

W

Weiqiang Chen

Department of Civil and Environmental Engineering and Rice Advanced Materials Institute, Ken Kennedy Institute, Rice University, 6100 Main Street

H

Huihua Wan

State Key Laboratory for Quality Ensurance and Sustainable Use of Dao‐di Herbs Key Laboratory of Beijing for Identification and Safety Evaluation of Chinese Medicine Institute of Chinese Materia Medica China Academy of Chinese Medical Sciences Beijing 100700 China

X

Xiangxiao Meng

State Key Laboratory for Quality Ensurance and Sustainable Use of Dao‐di Herbs Key Laboratory of Beijing for Identification and Safety Evaluation of Chinese Medicine Institute of Chinese Materia Medica China Academy of Chinese Medical Sciences Beijing 100700 China

X

Xuewen Zhu

State Key Laboratory for Quality Ensurance and Sustainable Use of Dao‐di Herbs Key Laboratory of Beijing for Identification and Safety Evaluation of Chinese Medicine Institute of Chinese Materia Medica China Academy of Chinese Medical Sciences Beijing 100700 China

Y

Yuhong Lu

State Key Laboratory of Bioactive Substance and Function of Natural Medicines NHC Key Laboratory of Biosynthesis of Natural Products CAMS Key Laboratory of Enzyme and Biocatalysis of Natural Drugs Institute of Materia Medica Chinese Academy of Medical Sciences and Peking Union Medical College Beijing 100050 China

Q

Qi Shen

Department of Cancer Institute, Xuzhou Medical University

C

Chunhong Jiang

State Key Laboratory of Innovative Natural Medicine and TCM Injections Jiangxi Qingfeng Pharmaceutical Co. Ltd. Ganzhou 341008 China

N

Ning Xie

S

Shilin Chen

Center for AIE Research, College of Materials Science and Engineering

M

Meirong Jia

State Key Laboratory of Bioactive Substance and Function of Natural Medicines, NHC Key Laboratory of Natural Products, CAMS Key Laboratory of Enzyme and Biocatalysis of Natural Drugs

W

Wei Sun