Synthesis of hydroxycinnamoyl shikimates and their role in monolignol biosynthesis

Padmakshan, Dharshana; Timokhin, Vitaliy I.; Lu, Fachuang; Schatz, Paul F.; Vanholme, Ruben; Boerjan, Wout; Ralph, John

doi:10.1515/hf-2021-0149

Title: Synthesis of hydroxycinnamoyl shikimates and their role in monolignol biosynthesis

Journal Article · Mon Dec 20 00:00:00 EST 2021 · Holzforschung

DOI:https://doi.org/10.1515/hf-2021-0149· OSTI ID:1846253

^[1];

^[2]; Schatz, Paul F. ^[3];

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^[2]

Wisconsin Energy Inst., Madison, WI (United States)
Wisconsin Energy Inst., Madison, WI (United States); Univ. of Wisconsin, Madison, WI (United States)
USDA-Agricultural Research Service, Madison, WI (United States)
VIB, Ghent (Belgium); Ghent Univ. (Belgium)

Hydroxycinnamoyl shikimates were reported in 2005 to be intermediates in monolignol biosynthesis. 3-Hydroxylation of p-coumarate, originally thought to occur via coumarate 3-hydroxylase (C₃H) from p-coumaric acid or its CoA thioester, was revealed to be via the action of coumaroyl shikimate 3'-hydroxylase (C₃'H) utilizing p-coumaroyl shikimate as the substrate, itself derived from p-coumaroyl-CoA via hydroxycinnamoyl-CoA: shikimate hydroxycinnamoyltransferase (HCT). The same HCT was conjectured to convert the product, caffeoyl shikimate, to caffeoyl-CoA to continue on the pathway starting with its 3-O-methylation. At least in some plants, however, a more recently discovered caffeoyl shikimate esterase (CSE) enzyme hydrolyzes caffeoyl shikimate to caffeic acid from which it must again produce its CoA thioester to continue on the monolignol biosynthetic pathway. HCT and CSE are therefore monolignol biosynthetic pathway enzymes that have provided new opportunities to misregulate lignification. To facilitate studies into the action and substrate specificity of C₃H/C₃'H, HCT, and CSE enzymes, as well as for metabolite authentication and for enzyme characterization, including kinetics, a source of authentic substrates and products was required. A synthetic scheme starting from commercially available shikimic acid and the four key hydroxycinnamic acids (p-coumaric, caffeic, ferulic, and sinapic acid) has been developed to provide this set of hydroxycinnamoyl shikimates for researchers.

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Research Organization:: Great Lakes Bioenergy Research Center (GLBRC), Madison, WI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: SC0018409

OSTI ID:: 1846253

Journal Information:: Holzforschung, Vol. 76, Issue 2; ISSN 0018-3830

Publisher:: de GruyterCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Synthesis of hydroxycinnamoyl shikimates and their role in monolignol biosynthesis

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