InChI=1S/C19H20N2O/c1- 2-11-9-21-17-8-14-12-5-3-4-6-16(12)20-19(14)18(21)7-13(11)15(17)10-22/h2-6,10,13,15,17-18,20H,7-9H2,1H3/b11-2-/t13-,15-,17-,18-/m0/s1 |
| MHASSCPGKAMILD-MIOJWWSHSA-N |
| C\C=C1\CN2[C@H]3Cc4c([nH]c5ccccc45)[C@@H]2C[C@@H]1[C@@H]3C=O |
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plant metabolite
Any eukaryotic metabolite produced during a metabolic reaction in plants, the kingdom that include flowering plants, conifers and other gymnosperms.
metabolite
Any intermediate or product resulting from metabolism. The term 'metabolite' subsumes the classes commonly known as primary and secondary metabolites.
(via alkaloid )
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View more via ChEBI Ontology
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16-Epivellosimine
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KEGG COMPOUND
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16-epivellosimine
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UniProt
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6894765
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Reaxys Registry Number
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Reaxys
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Yin W, Kabir MS, Wang Z, Rallapalli SK, Ma J, Cook JM (2010)
Enantiospecific total synthesis of the important biogenetic intermediates along the ajmaline pathway, (+)-polyneuridine and (+)-polyneuridine aldehyde, as well as 16-epivellosimine and macusine A.
The Journal of organic chemistry 75, 3339-3349 [PubMed:20392128]
[show Abstract]
The first stereospecific synthesis of polyneuridine aldehyde (6), 16-epivellosimine (7), (+)-polyneuridine (8), and (+)-macusine A (9) has been accomplished from commercially available d-(+)-tryptophan methyl ester. d-(+)-Tryptophan has served here both as the chiral auxiliary and the starting material for the synthesis of the common intermediate, (+)-vellosimine (13). This alkaloid was available in enantiospecific fashion in seven reaction vessels in 27% overall yield from d-(+)-trytophan methyl ester (14) via a combination of the asymmetric Pictet-Spengler reaction, Dieckmann cyclization, and a stereocontrolled intramolecular enolate-driven palladium-mediated cross-coupling reaction. A new process for this stereocontrolled intramolecular cross-coupling has been developed via a copper-mediated process. The initial results of this investigation indicated that an enolate-driven palladium-mediated cross-coupling reaction can be accomplished by a copper-mediated process which is less expensive and much easier to work up. An enantiospecific total synthesis of (+)-polyneuridine aldehyde (6), which has been proposed as an important biogenetic intermediate in the biosynthesis of quebrachidine (2), was then accomplished in an overall yield of 14.1% in 13 reaction vessels from d-(+)-tryptophan methyl ester (14). Aldehyde 13 was protected as the N(a)-Boc aldehyde 32 and then converted into the prochiral C(16)-quaternary diol 12 via the practical Tollens' reaction and deprotection. The DDQ-mediated oxidative cyclization and TFA/Et(3)SiH reductive cleavage served as protection/deprotection steps to provide a versatile entry into the three alkaloids polyneuridine aldehyde (6), polyneuridine (8), and macusine A (9) from the quarternary diol 12. The oxidation of the 16-hydroxymethyl group present in the axial position was achieved with the Corey-Kim reagent to provide the desired beta-axial aldehydes, polyneuridine aldehyde (6), and 16-epivellosimine (7) with 100% diastereoselectivity. | Pfitzner A, Stöckigt J (1983)
Characterization of polyneuridine aldehyde esterase, a key enzyme in the biosynthesis of sarpagine/ajmaline type alkaloids.
Planta medica 48, 221-227 [PubMed:17404987]
[show Abstract]
Polyneuridine aldehyde esterase (PNA-esterase) was isolated and partially purified from cell suspension cultures of RAUWOLFIA SERPENTINA B ENTH. The exceptionally high substrate specific enzyme catalyses the conversion of the monoterpenoid C (10-) into the C (9-)unit at the stage of polyneuridine aldehyde during the biosynthesis of sarpagine/ajmaline type alkaloids. The enzymatically formed compound is the new, labile indole alkaloid 16-epivellosimine. It is this alkaloid which functions as a branch point of the biogenetic routes leading to sarpagan and ajmalan type alkaloids. PNA-esterase occupies a key position in the biosynthesis of both alkaloid groups. |
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