Bioinspired Total Synthesis of Myltayloriones A‐B and Mylnudones A–D
Abstract
ABSTRACT Herein, we report the first asymmetric synthesis of the dimeric sesquiterpenoid myltayloriones A and B. The synthesis features a stereodivergent Echavarren Au‐catalyzed reaction that enables the synthesis of two subunits from a common dienyne precursor, followed by an endo ‐Diels–Alder heterodimerization. Additional key transformations include a ligand‐controlled Pd‐catalyzed reductive hydrogenolysis for C1 isomerization, and a metal‐catalyzed hydrogen atom transfer (MHAT)‐initiated Baran–Giese cyclization to forge a highly congested penta‐substituted cyclopropane. The selectivity of Pd‐catalyzed hydrogenolysis originates from two different oxidative addition pathways, as further elucidated by density functional theory (DFT) calculations. This synthetic work has enabled further investigation of the potent growth differentiation factor 15 (GDF15) inhibitory and insect antifeedant activity exhibited by myltaylorione A. Furthermore, the developed strategy enabled the concise synthesis of mylnudones A–D and revised the structures of mylnudones A and B.
Article Details
Authors (14)
Zong‐Xu Gao
State Key Laboratory of Discovery and Utilization of Functional Components in Traditional Chinese Medicine Key Laboratory of Chemical Biology (Ministry of Education) Shandong Basic Science Special Academic Zone (Pharmacy) Shandong University Jinan P. R. China
Xiao‐Xue Chen
State Key Laboratory of Discovery and Utilization of Functional Components in Traditional Chinese Medicine Key Laboratory of Chemical Biology (Ministry of Education) Shandong Basic Science Special Academic Zone (Pharmacy) Shandong University Jinan P. R. China
Yue‐Qing Zhang
State Key Laboratory of Discovery and Utilization of Functional Components in Traditional Chinese Medicine Key Laboratory of Chemical Biology (Ministry of Education) Shandong Basic Science Special Academic Zone (Pharmacy) Shandong University Jinan P. R. China
Jing Fan
Pei‐Lin Wu
State Key Laboratory of Discovery and Utilization of Functional Components in Traditional Chinese Medicine Key Laboratory of Chemical Biology (Ministry of Education) Shandong Basic Science Special Academic Zone (Pharmacy) Shandong University Jinan P. R. China
Ling‐Fei Hu
State Key Laboratory of Discovery and Utilization of Functional Components in Traditional Chinese Medicine Key Laboratory of Chemical Biology (Ministry of Education) Shandong Basic Science Special Academic Zone (Pharmacy) Shandong University Jinan P. R. China
Chenyingchun Su
Zhang‐Qin Xue
State Key Laboratory of Discovery and Utilization of Functional Components in Traditional Chinese Medicine Key Laboratory of Chemical Biology (Ministry of Education) Shandong Basic Science Special Academic Zone (Pharmacy) Shandong University Jinan P. R. China
Ming‐Zhu Zhu
State Key Laboratory of Discovery and Utilization of Functional Components in Traditional Chinese Medicine Key Laboratory of Chemical Biology (Ministry of Education) Shandong Basic Science Special Academic Zone (Pharmacy) Shandong University Jinan P. R. China
Pei‐Hong Fan
State Key Laboratory of Discovery and Utilization of Functional Components in Traditional Chinese Medicine Key Laboratory of Chemical Biology (Ministry of Education) Shandong Basic Science Special Academic Zone (Pharmacy) Shandong University Jinan P. R. China
Jiao‐Zhen Zhang
State Key Laboratory of Discovery and Utilization of Functional Components in Traditional Chinese Medicine Key Laboratory of Chemical Biology (Ministry of Education) Shandong Basic Science Special Academic Zone (Pharmacy) Shandong University Jinan P. R. China
Yan Zong
Department of Biomedical Engineering, College of Future Technology
Ze‐Jun Xu
State Key Laboratory of Discovery and Utilization of Functional Components in Traditional Chinese Medicine Key Laboratory of Chemical Biology (Ministry of Education) Shandong Basic Science Special Academic Zone (Pharmacy) Shandong University Jinan P. R. China
Hong‐Xiang Lou
State Key Laboratory of Discovery and Utilization of Functional Components in Traditional Chinese Medicine Key Laboratory of Chemical Biology (Ministry of Education) Shandong Basic Science Special Academic Zone (Pharmacy) Shandong University Jinan P. R. China