Variation on a theme: the structures and biosynthesis of specialized fatty acid natural products in plants

Abstract

SUMMARY Plants are able to construct lineage‐specific natural products from a wide array of their core metabolic pathways. Considerable progress has been made toward documenting and understanding, for example, phenylpropanoid natural products derived from phosphoenolpyruvate via the shikimate pathway, terpenoid compounds built using isopentyl pyrophosphate, and alkaloids generated by the extensive modification of amino acids. By comparison, natural products derived from fatty acids have received little attention, except for unusual fatty acids in seed oils and jasmonate‐like oxylipins. However, scattered but numerous reports show that plants are able to generate many structurally diverse compounds from fatty acids, including some with highly elaborate and unique structural features that have novel bioproduct functionalities. Furthermore, although recent work has shed light on multiple new fatty acid natural product biosynthesis pathways and products in diverse plant species, these discoveries have not been reviewed. The aims of this work, therefore, are to (i) review and systematize our current knowledge of the structures and biosynthesis of fatty acid‐derived natural products that are not seed oils or jasmonate‐type oxylipins, specifically, polyacetylenic, very‐long‐chain, and aromatic fatty acid‐derived natural products, and (ii) suggest priorities for future investigative steps that will bring our knowledge of fatty acid‐derived natural products closer to the levels of knowledge that we have attained for other phytochemical classes.

Genome-wide identification and expression analysis of 3-ketoacyl-CoA synthase gene family in rice (Oryza sativa L.) under cadmium stress

“…Very long-chain fatty acids (VLCFAs) are molecules with a hydrocarbon chain containing more than 18 carbon atoms, which are important components of plant cell membrane lipids, cutin wax, and seed storage lipids ( Scott et al., 2022 ). VLCFAs and their derivatives play an important role in plant growth and development, signal transduction, and adverse stress.…”

Genome-wide identification and expression analysis of the KCS gene family in soybean (Glycine max) reveal their potential roles in response to abiotic stress

“…VLCFAs and their derivatives, including alkanes, ketones, alcohols, aldehydes, and wax esters, are the main components of cuticular wax. Thus, their content and composition are tightly associated with plant growth, development, and stress tolerance capability ( Haslam and Kunst, 2013 ; Scott et al., 2022 ). In Arabidopsis, drought, salt and abscisic acid stress treatments lead to a significant increase in the amount of leaf cuticular wax ( Kosma et al., 2009 ).…”

“…composition are tightly associated with plant growth, development, stress tolerance capability (Haslam and Kunst, 2013;Scott et al, 2022). In Arabidopsis, drought, salt and abscisic acid stress treatments lead to a significant increase in the amount of leaf cuticular wax (Kosma et al, 2009).…”

“…Fatty acids with a hydrocarbon chain lengths of 20 or more carbon atoms are known as VLCFAs ( Scott et al., 2022 ). The VLCFAs and their derivatives are the main components of numerous lipids that function in specific cell/tissue types, such as triacylglycerols that accumulate in the seeds, sphingolipids, and phospholipids that are essential for membrane homeostasis, cuticular waxes deposited on plant aerial surfaces, and suberin monomers that are indispensable for root development ( Haslam and Kunst, 2013 ).…”

Comprehensive evolutionary analysis of the FAD2 gene family in representatives of campanulids: identification and characterization of candidate genes from the plant polyacetylene metabolism

“…Among the three biosynthetic pathways for PAs proposed in plants, the crepenynate pathway has been deemed to be a major one, and found only in campanulids, which gives rise to the majority of the known PAs [3,7]. Previous studies suggested that Fatty Acid Desaturase 2 (FAD2) [8] plays important roles in the initiation of PA biosynthesis in all lineages of campanulids investigated so far [9,10,11,12]. FAD2 is a member of the fatty acids desaturases family, usually catalyzes desaturation at the C-12 position (i.e., Δ 12 , this notation is used consistently throughout) of oleic acid to form linoleic acid on the endoplasmic reticulum [13].…”