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

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

  • Nat Plants. 2025 Sep;11(9):1903-1919. doi: 10.1038/s41477-025-02082-x.
Rui Zhai # 1,  Hongjuan Zhang # 1,  Yinpeng Xie # 1 2,  Shichao Zhang 1,  Fengli Zhou 1,  Xuan Du 3,  Weifeng Chen 4,  YanFang Yan 1 2,  Jing Zhang 1,  Pengmin Li 5 6,  Ross Atkinson 7,  Zhigang Wang 1,  Chengquan Yang 1,  Qingmei Guan 1 2,  Fengwang Ma 1 2,  Lingfei Xu 8 9
Affiliations

Affiliations

  • 1 College of Horticulture, Northwest A&F University, Yangling, Shaanxi, China.
  • 2 State Key Laboratory for Crop Stress Resistance and High-Efficiency Production/Shaanxi Key Laboratory of Apple, Northwest A&F University, Yangling, Shaanxi, China.
  • 3 Guangdong Provincial Key Laboratory for Plant Epigenetics, College of Life Sciences and Oceanography, Shenzhen University, Shenzhen, China.
  • 4 Hunan Horticultural Research Institute, Hunan Academy of Agricultural Sciences, Changsha, China.
  • 5 College of Horticulture, Northwest A&F University, Yangling, Shaanxi, China. lipm@nwsuaf.edu.cn.
  • 6 State Key Laboratory for Crop Stress Resistance and High-Efficiency Production/Shaanxi Key Laboratory of Apple, Northwest A&F University, Yangling, Shaanxi, China. lipm@nwsuaf.edu.cn.
  • 7 The New Zealand Institute for Plant and Food Research Limited, Auckland, New Zealand.
  • 8 College of Horticulture, Northwest A&F University, Yangling, Shaanxi, China. lingfxu2013@sina.com.
  • 9 State Key Laboratory for Crop Stress Resistance and High-Efficiency Production/Shaanxi Key Laboratory of Apple, Northwest A&F University, Yangling, Shaanxi, China. lingfxu2013@sina.com.
  • # Contributed equally.
PMID: 40913079 DOI: 10.1038/s41477-025-02082-x
Abstract

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 β-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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