Discovery and Biomimetic Synthesis of a Phloroglucinol‐Terpene Adduct Collection from <i>Baeckea frutescens</i> and Its Biogenetic Origin Insight
Shilin Luo, Lijun Hu, Xiao‐Jun Huang, Jun‐Cheng Su, Xuehua Shao, Lei Wang, Hanhong Xu, Chuang‐Chuang Li, Ying Wang, Wen‐Cai Ye
Abstract
A phloroglucinol-terpene adduct (PTA) collection consisting of twenty-four molecules featuring three skeletons was discovered from Baeckea frutescens. Inspired by its biosynthetic hypothesis, we synthesized this PTA collection by reductive activation of stable phloroglucinol precursors into highly reactive ortho-quinone methide (o-QM) intermediates and subsequently Diels-Alder cycloaddition. We also demonstrated, for the first time, the generation process of the active o-QM by performing dynamic NMR and HPLC-MS monitoring experiments. Moreover, the PTA collection showed significant antifeedant effect toward the Plutella xylostella larvae.