Synthesis and Biochemical Evaluation of an Artificial, Fluorescent Glucosinolate (GSL)

Glindemann, Carina Patrizia; Backenköhler, Anita; Strieker, Matthias; Wittstock, Ute; Klahn, Philipp

doi:10.1002/cbic.201900148

Cited by 15 publications

(24 citation statements)

References 42 publications

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“…Camalexin, cyanogenic 4-OH-ICN metabolite, and indole glucosinolates are three classes of known tryptophan-derived defense metabolites. Among them, camalexin and 4-OH-ICN, produced through CYP71A12 and CYP71A13, were shown to act as specialized defense compounds against aphids and a variety of plant pathogens (Thomma et al, 1999;Bohman et al, 2004;Kettles et al, 2013;Glindemann et al, 2019;. Here, we demonstrated that defense compounds synthesized through CYP71A12-and CYP71A13dependent pathways are not protecting Arabidopsis from mite herbivory, Fig.…”

Section: Discussionmentioning

confidence: 53%

“…The copyright holder for this preprint this version posted February 3, 2021. ; https://doi.org/10.1101/2021.02.03.429630 doi: bioRxiv preprint al., 2014). CYP79B2 and CYP79B3 are required for the conversion of tryptophan to indole-3-acetaldoxime (IAOx) that is further processed by CYP71A13, CYP71A12, and CYP83B1 to initiate biosynthesis of camalexin, cyanogenic metabolite 4-OH-ICN and indole glucosinolate (IG) defense compounds, respectively (Zhao et al, 2002;Vik et al, 2018;Glindemann et al, 2019;. 3-Indolylmethyl glucosinolate (I3M) is a parental indole glucosinolate that is further hydroxylated by cytochromes P450 of the CYP81 family and methylated by IG methyltransferases.…”

Section: Introductionmentioning

confidence: 99%

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Multiple indole glucosinolates and myrosinases defend Arabidopsis against Tetranychus urticae herbivory

et al. 2021

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Arabidopsis (Arabidopsis thaliana) defenses against herbivores are regulated by the jasmonate hormonal signaling pathway, which leads to the production of a plethora of defense compounds. Arabidopsis defense compounds include tryptophan-derived metabolites which limit Arabidopsis infestation by the generalist herbivore two-spotted spider mite, Tetranychus urticae. However, the phytochemicals responsible for Arabidopsis protection against T. urticae are unknown. Here, we used Arabidopsis mutants disrupted in the synthesis of tryptophan-derived secondary metabolites to identify phytochemicals involved in the defense against T. urticae. We show that of the three tryptophan-dependent pathways found in Arabidopsis, the indole glucosinolate pathway is necessary and sufficient to assure tryptophan-mediated defense against T. urticae. We demonstrate that all three indole glucosinolates can limit T. urticae herbivory, but that they must be processed by myrosinases to hinder T. urticae oviposition. Putative indole glucosinolate breakdown products were detected in mite-infested leaves, suggesting in planta processing by myrosinases. Finally, we demonstrate that besides indole glucosinolates, there are additional jasmonate-regulated defenses that control T. urticae herbivory. Together, our results reveal the complexity of Arabidopsis defenses against T. urticae that rely on multiple indole glucosinolates, specific myrosinases, and additional jasmonate-dependent defenses.

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Section: Discussionmentioning

confidence: 53%

Section: Introductionmentioning

confidence: 99%

Multiple indole glucosinolates and myrosinases defend Arabidopsis against Tetranychus urticae herbivory

et al. 2021

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“…Retrosynthetic analysis for nitrabirine (5) Subsequent substitution of the chloride in the presence of sodium azide in dimethylformamide at 80°C yielded the known 16 azide 16 in 83% yield. 17 Reduction of the β-oxo group of 16 in the presence of sodium borohydride in ethanol gave the known 18 secondary alcohols 15 and 15' in a 1:1 mixture of the diastereomers. Finally, the reduction of the azide moieties of 15 and 15' to the amino groups in the presence of Zn/NH4Cl in ethanol:water/3:1 19 followed by spontaneous ring closure to the δ-spiro lactame at 80°C led to a 2:1-mixture of the known 11 diastereomers 14 and 14', which could be separated by flash column chromatography through silica gel and were obtained in 35% and 17%, respectively.…”

Section: Resultsmentioning

confidence: 99%

Total Synthesis via Biomimetic Late-stage Heterocyclization, Assignment of the Relative Configuration and Biological Evalu-ation of the Nitraria Alkaloid (±)-Nitrabirine

Kagho

Hintersatz

Ihle

et al. 2021

Preprint

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The racemic total synthesis of nitrabirine (5) together with its previously undescribed epimer 2-epi nitrabirine (5') is accomplished via a six-step route based on a biomimetic late-stage heterocyclization. This allowed the assignment of the relative configuration of nitrabirine by the lanthanide-induced shifts (LIS) experiment, later on confirmed by X-ray diffraction of obtained single crystals. Furthermore, oxidation studies demonstrated that the direct N-oxidation of nitrabirine does not yield nitrabirine N-oxide as reported earlier. In contrast, the reaction of hydrogen peroxide with nitrabirine (5) yields the salt 24' whereas, under the same conditions, 2-epi nitrabirine (5') surprisingly leads to a beforetime uncharacterized product 22. Finally, a Fischer-Indole reaction gave access to novel tetracyclic nitrabirine derivatives 26a-d. A comprehensive biological evaluation of nitrabirine (5), 2-epi nitrabirine (5'), and all derivatives synthesized in this study revealed general biofilm dispersal effects against Candida albicans. Moreover, specific compounds showed moderate antibacterial as well as potent cytotoxic activities.

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“…Camalexin, cyanogenic 4-OH-ICN metabolite, and indole glucosinolates are three classes of known tryptophan-derived defense metabolites. Among them, camalexin and 4-OH-ICN, produced through CYP71A12 and CYP71A13, were shown to act as specialized defense compounds against aphids and a variety of plant pathogens (Thomma et al, 1999; Bohman et al, 2004; Ferrari et al, 2007; Sanchez-Vallet et al, 2010; Schlaeppi et al, 2010; Kettles et al, 2013; Glindemann et al, 2019; Pastorczyk et al, 2020). Here, we demonstrated that defense compounds synthesized through CYP71A12- and CYP71A13-dependent pathways are not protecting Arabidopsis from mite herbivory, Fig.…”

Section: Discussionmentioning

confidence: 99%

“…Aliphatic glucosinolates are not effective against mites, however, mite fitness increases on the cyp79b2 cyp79b3 mutant plants, indicating that the Trp-derived secondary metabolite(s) restrict mite herbivory (Zhurov et al, 2014). CYP79B2 and CYP79B3 are required for the conversion of tryptophan to indole-3-acetaldoxime (IAOx) that is further processed by CYP71A13, CYP71A12, and CYP83B1 to initiate biosynthesis of camalexin, cyanogenic metabolite 4-OH-ICN and indole glucosinolate (IG) defense compounds, respectively (Zhao et al, 2002; Sanchez-Vallet et al, 2010; Rajniak et al, 2015; Vik et al, 2018; Glindemann et al, 2019; Pastorczyk et al, 2020). 3-Indolylmethyl glucosinolate (I3M) is a parental indole glucosinolate that is further hydroxylated by cytochromes P450 of the CYP81 family and methylated by IG methyltransferases.…”

Section: Introductionmentioning

confidence: 99%

Multiple indole glucosinolates and myrosinases defend Arabidopsis againstTetranychus urticaeherbivory

Widemann¹,

Bruinsma²,

Walshe-Roussel

et al. 2021

Preprint

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Arabidopsis defenses against herbivores are regulated by the jasmonate hormonal signaling pathway, which leads to the production of a plethora of defense compounds, including tryptophan-derived metabolites produced through CYP79B2/CYP79B3. Jasmonate signaling and CYP79B2/CYP79B3 limit Arabidopsis infestation by the generalist herbivore two-spotted spider mite, Tetranychus urticae. However, the phytochemicals responsible for Arabidopsis protection against T. urticae are unknown. Here, using Arabidopsis mutants that disrupt metabolic pathways downstream of CYP79B2/CYP79B3, and synthetic indole glucosinolates, we identified phytochemicals involved in the defense against T. urticae. We show that Trp-derived metabolites depending on CYP71A12 and CYP71A13 are not affecting mite herbivory. Instead, the supplementation of cyp79b2 cyp79b3 mutant leaves with the 3-indolylmethyl glucosinolate and its derived metabolites demonstrated that the indole glucosinolate pathway is sufficient to assure CYP79B2/CYP79B3-mediated defenses against T. urticae. We demonstrate that three indole glucosinolates can limit T. urticae herbivory, but that they have to be processed by the myrosinases to hinder T. urticae oviposition. Finally, the supplementation of the mutant myc2 myc3 myc4 with indole glucosinolates indicated that the transcription factors MYC2/MYC3/MYC4 induce additional indole glucosinolate-independent defenses that control T. urticae herbivory. Together, these results reveal the complexity of Arabidopsis defenses against T. urticae that rely on multiple indole glucosinolates, specific myrosinases, and additional MYC2/MYC3/MYC4-dependent defenses.

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Synthesis and Biochemical Evaluation of an Artificial, Fluorescent Glucosinolate (GSL)

Cited by 15 publications

References 42 publications

Multiple indole glucosinolates and myrosinases defend Arabidopsis against Tetranychus urticae herbivory

Multiple indole glucosinolates and myrosinases defend Arabidopsis against Tetranychus urticae herbivory

Total Synthesis via Biomimetic Late-stage Heterocyclization, Assignment of the Relative Configuration and Biological Evalu-ation of the Nitraria Alkaloid (±)-Nitrabirine

Multiple indole glucosinolates and myrosinases defend Arabidopsis againstTetranychus urticaeherbivory

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