The Absolute Configuration of the Pyrrolosesquiterpenoid Glaciapyrrol A

Riclea, Ramona; Dickschat, Jeroen S.

doi:10.1002/chem.201101139

Cited by 17 publications

(19 citation statements)

References 16 publications

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“…Although the genes responsible for heronapyrrole biosynthesis have not been identified yet, it is nevertheless possible to speculate on key aspects of this biosynthetic pathway, particularly those oxidative transformations that generate structural diversity [6–9] in the farnesyl side chain. For example, it is reasonable to conclude that 4-farnesylated 2-nitropyrrole 1 (Scheme 1) – arising from the action of a farnesyl transferase [10–11] on a suitable 2-nitropyrrole precursor – is a highly plausible common precursor for all heronapyrroles.…”

Section: Resultsmentioning

confidence: 99%

Heronapyrrole D: A case of co-inspiration of natural product biosynthesis, total synthesis and biodiscovery

Schmidt

Khalil

Capon

et al. 2014

Beilstein J. Org. Chem.

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SummaryThe heronapyrroles A–C have first been isolated from a marine-derived Streptomyces sp. (CMB-0423) in 2010. Structurally, these natural products feature an unusual nitropyrrole system to which a partially oxidized farnesyl chain is attached. The varying degree of oxidation of the sesquiterpenyl subunit in heronapyrroles A–C provoked the hypothesis that there might exist other hitherto unidentified metabolites. On biosynthetic grounds a mono-tetrahydrofuran-diol named heronapyrrole D appeared a possible candidate. We here describe a short asymmetric synthesis of heronapyrrole D, its detection in cultivations of CMB-0423 and finally the evaluation of its antibacterial activity. We thus demonstrate that biosynthetic considerations and the joint effort of synthetic and natural product chemists can result in the identification of new members of a rare class of natural products.

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Section: Resultsmentioning

confidence: 99%

Heronapyrrole D: A case of co-inspiration of natural product biosynthesis, total synthesis and biodiscovery

Schmidt

Khalil

Capon

et al. 2014

Beilstein J. Org. Chem.

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“…(NPS008187) by Macherla et al [161]. The only established total synthesis has been developed by the Dickschat group in 2011 [162] using a type A Ru(VIII)-catalyzed oxidative cyclization as the key step (Scheme 21). …”

Section: Reviewmentioning

confidence: 99%

The direct oxidative diene cyclization and related reactions in natural product synthesis

Adrian¹,

Gross²,

Stark³

2016

Beilstein J. Org. Chem.

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SummaryThe direct oxidative cyclization of 1,5-dienes is a valuable synthetic method for the (dia)stereoselective preparation of substituted tetrahydrofurans. Closely related reactions start from 5,6-dihydroxy or 5-hydroxyalkenes to generate similar products in a mechanistically analogous manner. After a brief overview on the history of this group of transformations and a survey on mechanistic and stereochemical aspects, this review article provides a summary on applications in natural product synthesis. Moreover, current limitations and future directions in this area of chemistry are discussed.

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“…For the unambiguous elucidation of the unknown relative configuration of glaciapyrrole A ( 7), we first embarked on the total synthesis of all four of its (racemic) diastereomers that were possible from variations of the relative configurations at the three stereogenic centers (Scheme 1). 29 For this purpose, a ruthenium-catalyzed method for the oxidative cyclization of geranyl or neryl benzoate, developed by Stark and co-workers, was used. 30 This method gave access to all four diastereomeric tetrahydrofurancontaining diols 8.…”

Section: Total Synthesis Of Glaciapyrrole a And Tricho-acorenolmentioning

confidence: 99%

Microbial Terpenes: A Perspective on Their Chemistry and Biosynthesis

Citron

Dickschat

2014

Synlett

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This personal account summarizes our ongoing work on the bioorganic chemistry of diverse microbial terpenoids. First, two selected total syntheses that were recently completed in our group are presented. We then show how the fundamental technique for our analytical work, closed-loop stripping apparatus (CLSA) in combination with gas chromatography/mass spectrometry (GC/MS), can be used to efficiently identify volatile natural products from various bacteria and fungi. The largest compound class among these volatiles is the terpenes. The CLSA technique can also be successfully applied to study interesting problems of the sometimes puzzling biosynthetic pathways towards terpenes. For this purpose we have developed two new CLSA-based methods, the first using 13 C-labeled precursors in feeding studies which allow for structure elucidations of microgram amounts of terpenes in complex headspace mixtures, and the second, a genome-mining approach via heterologous expression for the rapid chemical characterization of bacterial terpene cyclases. Recent developments in our laboratory include mechanistic investigations based on enzyme structural data in combination with site-specific mutations of terpene cyclases. 1 Introduction 2 Total Synthesis of Glaciapyrrole A and Tricho-acorenol 3 Feeding Experiments with Deuterated Precursors 4 The IspH Reaction 5 Feeding Experiments with 13 C-Labeled Precursors 6 Genome Mining and Closed-Loop Stripping Apparatus 7 Conclusion

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The Absolute Configuration of the Pyrrolosesquiterpenoid Glaciapyrrol A

Cited by 17 publications

References 16 publications

Heronapyrrole D: A case of co-inspiration of natural product biosynthesis, total synthesis and biodiscovery

Heronapyrrole D: A case of co-inspiration of natural product biosynthesis, total synthesis and biodiscovery

The direct oxidative diene cyclization and related reactions in natural product synthesis

Microbial Terpenes: A Perspective on Their Chemistry and Biosynthesis

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