Pyrrovobasine, hybrid alkylated pyrraline monoterpene indole alkaloid pseudodimer discovered using a combination of mass spectral and NMR-based machine learning annotations

Fouotsa, Hugues; Mkounga, Pierre; Lannang, Alain Méli; Vanheuverzwijn, Jérôme; Zhou, Zhanpeng; Leblanc, Karine; Rharrabti, Somia; Nkengfack, Augustin Ephrem; Gallard, Jean‐François; Fontaine, Véronique; Meyer, Franck; Poupon, Erwan; Pogam, Pierre Le; Beniddir, Mehdi A.

doi:10.1039/d1ob01791h

Cited by 5 publications

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“…In such context, molecular networking strategies have proved useful to select natural material deserving deeper chemical studies as well as to streamline the isolation of compounds of interest through a rational, hypothesis-driven workflow 21 . This provides new opportunities to focus on minor, interesting compounds from deeply-dug plant material 22 , 23 . Nevertheless, the success of this dereplicative strategy primarily depends on the availability of reference tandem mass spectra uploaded to the GNPS spectral libraries 7 .…”

Section: Background and Summarymentioning

confidence: 99%

Implementation of a MS/MS database for isoquinoline alkaloids and other annonaceous metabolites

et al. 2022

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This data descriptor reports on the upload to a public repository (GNPS) of the IQAMDB, IsoQuinoline and Annonaceous Metabolites Data Base, comprising 320 tandem mass spectra. This project originated from our in-house collection of isoquinolines. The diversity of compounds included in this database was further extended through the contribution of two additional laboratories involved in isoquinoline alkaloids research: University of Angers and University of Manaus. The generated MS/MS data were processed and annotated on an individual basis to promote their straightforward reuse by natural product chemists interested in either the description of new isoquinoline alkaloids or the dereplication of isoquinoline-containing samples. The interest of the current repertoire for dereplication purposes has been validated based on the molecular networking of the well-investigated plant model Annona montana against the IQAMDB‐implemented GNPS.

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Section: Background and Summarymentioning

confidence: 99%

Implementation of a MS/MS database for isoquinoline alkaloids and other annonaceous metabolites

et al. 2022

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“…Interestingly, the methyl ester on the vobasine skeleton shows a signal around 2.5 ppm in 1 H NMR. 1 This peak is shifted to a higher field than that of the normal methyl ester. This is presumably due to the shielding effect of the indole moiety of the vobasine skeleton, which covers the methyl ester moiety and, thus, shifts it to a higher magnetic field.…”

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“…The regioselectivity and stereoselectivity of the introduction of the tryptamine derivative in the vobasine skeleton must be controlled, and we speculated that the regioselectivity of the tryptamine derivative would be C2-selective on the basis of its electron density. Interestingly, the methyl ester on the vobasine skeleton shows a signal around 2.5 ppm in 1 H NMR . This peak is shifted to a higher field than that of the normal methyl ester.…”

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“…The plausible biosynthetic pathway of pyrrovobasine ( 1 ) proposed by Bennidir and co-workers is shown in Figure B . After removal of the alcohol moiety of vobasinol ( 7 ), the C2 position of tryptamine derivative 9 with the pyrraline structure is linked to activated vobasinol derivative 3 to form pyrrovobasine ( 1 ).…”

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“…P yrrovobasine ( 1) is an indole alkaloid with a pseudodimer structure isolated from Voacanga africana stem bark extracts, mainly in tropical Africa, by Beniddir and co-workers in 2022 (Figure 1A). 1 It is structurally characterized by a pyrraline structure on the complex linkage of tryptophan and tryptamine, which is unusual for a natural product. The total synthesis of pyrrovobasine (1) has not yet been reported.…”

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Yu,

Nakamura

2023

JACS Au

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From the Spectroscopic Reassessment of Authentic Alkaloid Samples to the Molecular Networking-Guided Discovery of Criophylline-Related Analogues from Callichilia inaequalis

et al. 2023

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The molecular network-guided exploration of the alkaloid extract of Callichilia inaequalis stems revealed a cluster attributed tentatively to dimeric monoterpene indole alkaloids of the rare criophylline subtype, initiating the dual study reported herein. A patrimonial-themed portion of this work was aimed at performing a spectroscopic reassessment of criophylline (1), a monoterpene bisindole alkaloid for which the nature of the inter-monomeric connectivity and configurational assignments have remained dubious. A targeted isolation of the entity annotated as criophylline (1) was undertaken to strengthen the available analytical evidence. An extensive set of spectroscopic data was acquired from the authentic sample of criophylline (1a) isolated earlier by Cavé and Bruneton. These spectroscopic studies proved the samples to be identical, and the complete structure of criophylline could be assigned, half a century after it was first isolated. The absolute configuration of andrangine (2) was also ascertained based on a TDDFT-ECD approach from the authentic sample. The forward-looking aspect of this investigation resulted in the characterization of two new criophylline derivatives from C. inaequalis stems, namely, 14′-hydroxycriophylline (3) and 14′-O-sulfocriophylline (4). Their structures, including absolute configurations, were elucidated by analysis of NMR and MS spectroscopic data and by ECD analysis. Notably, 14′-O-sulfocriophylline (4) is the first sulfated monoterpene indole alkaloid to have been reported. The antiplasmodial activity against the chloroquine-resistant strain of Plasmodium falciparum FcB1 was determined for criophylline and its two new analogues.

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Pyrrovobasine, hybrid alkylated pyrraline monoterpene indole alkaloid pseudodimer discovered using a combination of mass spectral and NMR-based machine learning annotations

Abstract: A new vobasine-tryptamine-based monoterpene indole alkaloid pseudodimer was isolated from the stem bark of Voacanga africana. As a minor constituent occurring in a thoroughly investigated plant, this molecule was targeted...

Cited by 5 publications

References 44 publications

Implementation of a MS/MS database for isoquinoline alkaloids and other annonaceous metabolites

Implementation of a MS/MS database for isoquinoline alkaloids and other annonaceous metabolites

Short, Scalable Access to Pyrrovobasine

From the Spectroscopic Reassessment of Authentic Alkaloid Samples to the Molecular Networking-Guided Discovery of Criophylline-Related Analogues from Callichilia inaequalis

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