Structure complete de la raucaffrinoline et filiation avec la vomilenine

Libot, Francine; Kunesch, Nicole; Poisson, Jacques

doi:10.1016/0031-9422(80)85163-6

Cited by 29 publications

(42 citation statements)

References 10 publications

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“…To identify the reaction products, a large‐scale reaction was carried out, and the major product was characterized by NMR analysis (COSY, NOESY, HMBC, HSQC). Both 1 H and 13 C chemical shifts were in good agreement with previously reported data for vomilenine (Figure , Figure S6, Table S1) . 5437 was therefore designated vinorine hydroxylase (VH).…”

Section: Figuresupporting

confidence: 89%

“…All biosynthetic transformations leading from strictosidine to ajmaline have been detected in enzyme fractions from Rauwolfia cell culture, though only six biosynthetic genes have been cloned and characterized (Figure ) . Several studies showed that vomilenine is an ajmaline biosynthetic intermediate that is produced through selective hydroxylation of vinorine at the C‐21 position by Rauwolfia cell culture extracts (Figure ) . However, no enzyme isolated from R. serpentina has shown this activity …”

Section: Figurementioning

confidence: 99%

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Dual Catalytic Activity of a Cytochrome P450 Controls Bifurcation at a Metabolic Branch Point of Alkaloid Biosynthesis in Rauwolfia serpentina

et al. 2017

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Plants create tremendous chemical diversity from as ingle biosynthetic intermediate.I np lant-derived ajmalan alkaloid pathways, the biosynthetic intermediate vomilenine can be transformed into the anti-arrhythmic compound ajmaline,o ra lternatively,c an isomerizet of orm perakine,a n alkaloid with astructurally distinct scaffold. Here we report the discovery and characterization of vinorine hydroxylase,acytochrome P450 enzyme that hydroxylates vinorine to form vomilenine,w hich was found to exist as am ixture of rapidly interconverting epimers.S urprisingly,t his cytochrome P450 also catalyzest he non-oxidative isomerization of the ajmaline precursor vomilenine to perakine. This unusual dual catalytic activity of vinorine hydroxylase therebyp rovides ac ontrol mechanism for the bifurcation of these alkaloid pathwayb ranches.T his discovery highlights the unusual catalytic functionality that has evolved in plant pathways.

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Section: Figuresupporting

confidence: 89%

Section: Figurementioning

confidence: 99%

Dual Catalytic Activity of a Cytochrome P450 Controls Bifurcation at a Metabolic Branch Point of Alkaloid Biosynthesis in Rauwolfia serpentina

et al. 2017

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“…A number of alkaloids are known which belong to the sarpagineajmaline series, and share this unique feature. 5b These include the sarpagine alkaloids 10-hydroxy dihydroperaksine ( 3 ), 4 O-acetyl preperakine ( 4 ), 5,6 and the ajmaline-related alkaloids perakine ( 5 ) 5b,7,8 and raucaffrinoline ( 6 ) 5b,7,9 illustrated in Figure 1, as well as macrosalhine chloride, 5 peraksine, 5 verticillatine, 5 10-methoxyperakine, 5b,7 and vincawajine. 5b,7 No enantiospecific total synthesis of this class of sarpagine-ajmaline alkaloids has appeared to date.…”

mentioning

confidence: 99%

Regiospecific, Enantiospecific Total Synthesis of C-19 Methyl Substituted Sarpagine Alkaloids Dihydroperaksine-17-al and Dihydroperaksine

Edwankar

Deschamps

et al. 2011

Org. Lett.

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The optically active tetracyclic ketone 8 was converted into the pentacylic core 14 of the C-19 methyl substituted Na-H sarpagine and ajmaline alkaloids via a critical haloboration reaction. The ketone 14 was then employed in the total synthesis of 19(S),20(R)-dihydroperaksine-17-al (1) and 19(S),20(R)-dihydroperaksine (2). The key regioselective hydroboration and controlled oxidation-epimerization sequence developed in this approach should provide a general method to functionalize the C(20)-C(21) double bond in the ajmaline-related indole alkaloids.

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“…The JR (CHC13) spectrum showed strong absorptions at 1720 cm' (ester carbonyl), 2880 cm (C-H), 3350 cm' (N-H) and 1620 cm (C = C). The HRMS afforded the molecular ion peak at m/z 350.1626 (99%) leading to the molecular formula (C = C), 2900 (c-H), 3350 (N-H (11)(12)(13)(14). The 13C-NMR spectra of both alkaloids are consistent with the structures proposed earlier (8-10).…”

Section: Resultsmentioning

confidence: 99%