Naturally impaired side-chain shortening of aromatic 3-ketoacyl-CoAs reveals the biosynthetic pathway of plant acetophenones

文献类型： 外文期刊

第一作者： Zhai, Rui

作者： Zhai, Rui;Zhang, Hongjuan;Xie, Yinpeng;Zhang, Shichao;Zhou, Fengli;Yan, Yanfang;Zhang, Jing;Li, Pengmin;Wang, Zhigang;Yang, Chengquan;Guan, Qingmei;Ma, Fengwang;Xu, Lingfei;Xie, Yinpeng;Yan, Yanfang;Li, Pengmin;Guan, Qingmei;Ma, Fengwang;Xu, Lingfei;Du, Xuan;Chen, Weifeng;Atkinson, Ross

作者机构：

期刊名称：NATURE PLANTS （ 影响因子：13.6； 五年影响因子：17.0 ）

ISSN： 2055-026X

年卷期： 2025 年

页码：

收录情况： SCI

摘要： Acetophenones, which show scattered distribution across phylogenetically distant plants and fungi, play diverse roles in plant-plant, plant-insect, plant-microbiome and even animal-insect interactions. However, the enzymatic basis of acetophenone biosynthesis in plants remains unknown. Here we elucidate the complete biosynthetic pathway of picein (4-hydroxyacetophenone glucoside) from 4-coumaroyl-CoA using pear (Pyrus) as a study system. We demonstrate that in certain pear cultivars, the acetophenone moiety originates from an impaired side-chain shortening reaction of an aromatic 3-ketoacyl-CoA intermediate, a key step in the beta-oxidative biosynthesis of benzoic acid. This impairment results from a loss-of-function mutation in a peroxisomal 3-ketoacyl-CoA thiolase. The accumulated aromatic 3-ketoacyl-CoA is subsequently hydrolysed by a thioesterase and undergoes spontaneous decarboxylation to yield the acetophenone moiety. This rare metabolic phenomenon highlights that not only neofunctionalization but also loss-of-function mutations can drive diversification in plant secondary metabolism. Forward genetic approaches are powerful to shed light on such 'hidden' or recessive pathways in plants.

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