194346-16-2Relevant academic research and scientific papers
Controlling a structural branch point in ergot alkaloid biosynthesis
Cheng, Johnathan Z.,Coyle, Christine M.,Panaccione, Daniel G.,O'Connor, Sarah E.
, p. 12835 - 12837 (2010)
The ergot alkaloids are a diverse class of fungal-derived indole alkaloid natural products with potent pharmacological activities. The biosynthetic intermediate chanoclavine-I aldehyde 1 represents a branch point in ergot biosynthesis. Ergot alkaloids festuclavine 2 and agroclavine 3 derive from alternate enzymatic pathways originating from the common biosynthetic precursor chanoclavine-I aldehyde 1. Here we show that while the Old Yellow Enzyme homologue EasA from the ergot biosynthetic gene cluster of Aspergillus fumigatus acts on chanoclavine-I aldehyde 1 to yield festuclavine 2, EasA from Neotyphodium lolii, in contrast, produces agroclavine 3. Mutational analysis suggests a mechanistic rationale for the switch in activity that controls this critical branch point of ergot alkaloid biosynthesis.
New insights into ergot alkaloid biosynthesis in Claviceps purpurea: An agroclavine synthase EasG catalyses, via a non-enzymatic adduct with reduced glutathione, the conversion of chanoclavine-I aldehyde to agroclavine
Matuschek, Marco,Wallwey, Christiane,Xie, Xiulan,Li, Shu-Ming
, p. 4328 - 4335 (2011)
Ergot alkaloids are indole derivatives with diverse structures and biological activities. They are produced by a wide range of fungi with Claviceps purpurea as the most important producer for medical use. Chanoclavine-I aldehyde is proposed as a branch point via festuclavine or pyroclavine to clavine-type alkaloids in Trichocomaceae and via agroclavine to ergoamides and ergopeptines in Clavicipitaceae. Here we report the conversion of chanoclavine-I aldehyde to agroclavine by EasG from Claviceps purpurea, a homologue of the festuclavine synthase FgaFS in Aspergillus fumigatus, in the presence of reduced glutathione and NADPH. EasG comprises 290 amino acids with a molecular mass of about 31.9 kDa. The soluble monomeric His6-EasG was purified after overproduction in E. coli by affinity chromatography and used for enzyme assays. The structure of agroclavine was unequivocally elucidated by NMR and MS analyses.
Regioselective Direct C-4 Functionalization of Indole: Total Syntheses of (-)-Agroclavine and (-)-Elymoclavine
Lv, Jianbo,Wang, Bin,Yuan, Kuo,Wang, Yuan,Jia, Yanxing
, p. 3664 - 3667 (2017)
An efficient rhodium-catalyzed method for direct C-H functionalization at the C4 position of unprotected indoles has been developed. The utility of this method is demonstrated by the concise total syntheses of agroclavine and elymoclavine in a divergent manner. These syntheses feature a Pd-catalyzed asymmetric allylic alkylation reaction to assemble the triyclic indole moiety, and a ring-closing metathesis reaction to form the D ring.
Genes and processes for the production of clavine-type alkaloids
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, (2018/01/11)
Microorganisms and processes for the recombinant manufacture of clavine-type alkaloids such as cycloclavine, festuclavine, agroclavine, chanoclavine and chanoclavine aldehyde, as well as polypeptides, polynucleotides and vectors comprising such polynucleotides which can be applied in a method for the manufacture of clavine-type alkaloids are provided.
Synthetic studies directed toward ergot alkaloids, (±)-6,7-secoagroclavine, (±)-chanoclavine-1, (±)-chanoclavine-II, and (±)-agroclavine-I, by an efficient and common synthetic route
Yamada, Fumio,Makita, Yoshihiko,Somei, Masanori
, p. 599 - 620 (2008/03/12)
Novel three synthetic routes to (±)-6,7-secoagroclavine were developed from either methyl 3-(3-formylindol-4-yl)acrylate, indole-4-carbaldehyde, or 4-iodoindole-3-carbaldehyde. The total syntheses of (±)-chanoclavine-I, (±)-chanoclavine-II, and (±)-agroclavine-I were accomplished as well from the synthetic intermediates involved in the synthesis of (±)-6,7-secoagroclavine, culminating in establishing an efficient and common synthetic method for ergot alkaloids.
Simple total syntheses of (-)-ergot alkaloids and their (+)-enantiomers by a common synthesis method utilizing optical resolution
Somei, Masanori,Nakagawa, Kyoko
, p. 1263 - 1266 (2007/10/03)
The first and simple total syntheses of (-)-isochanoclavine-1 ((-)-1b), (-)-agroclavine ((-)-3), (-)-agroclavine-1 ((-)-4), and (-)-norchanoclavine-1 ((-)-5c) and their (+)-enantiomers are achieved from indole-3-carboxaldehyde (8) by a common synthesis method utilizing optical resolution. Absolute configuration of (-)-agroclavine-1 is determined to be 5R and 10S for the first time. Preparations of both enantiomers of chanoclavine-1 (1c) are also included.
TOTAL SYNTHESES OF (+/-)-AGROCLAVINE-I, (+/-)-6-NOR-CHANOCLAVINE-II, AND (+/-)-CHANOCLAVINE-II
Somei, Masanori,Yamada, Fumio,Makita, Yoshihiko
, p. 895 - 898 (2007/10/02)
The first total syntheses of (+/-)-6-nor-chanoclavine-II and (+/-)-chanoclavine-II are achieved.Total synthesis of (+/-)-agroclavine-I is also reported.
SHORT-STEP SYNTHESIS OF THE ERGOT ALKALOIDS, (+/-)-NORCHANOCLAVINE-I, (+/-)-CHANOCLAVINE-I, (+/-)-ISOCHANOCLAVINE-I, and (+/-)-AGROCLAVINE
Somei, Masanori,Makita, Yoshihiko,Yamada, Fumio
, p. 948 - 950 (2007/10/02)
The simple total synthesis of the ergot alkaloids, (+/-)-norchanoclavine-I, (+/-)-chanoclavine-I, (+/-)-isochanoclavine-I, and (+/-)-agroclavine was achieved by a practical and common synthesis method.A new regio-selective oxidation of the Z-methyl group of the isoprenyl system with selenium dioxide is described.Keywords - (+/-)-norchanoclavine-I; (+/-)-norisochanoclavine-I; (+/-)-chanoclavine-I; (+/-)-isochanoclavine-I; (+/-)-agroclavine; ergot alkaloid; total synthesis; common synthesis method; new oxidation
