Details
| Original language | English |
|---|---|
| Pages (from-to) | 5582-5591 |
| Number of pages | 10 |
| Journal | European Journal of Organic Chemistry |
| Volume | 2017 |
| Issue number | 37 |
| Publication status | Published - 28 Aug 2017 |
Abstract
The elansolids A1/A2 and B1–B3 are secondary metabolites formed by the gliding bacterium Chitinophaga sancti. They show antibacterial activity against Gram-positive bacteria. It has been proposed that the biosynthesis of the tetrahydroindane unit involves an intramolecular Diels–Alder cycloaddition (IMDA). To study the biosynthetic proposal, the influence of an oxygen functionality at C-20, the regiochemistry of the allylic alcohol precursor, and the nature of the phenol group were investigated. The oxygen functionality at C-20 has a profound effect on the outcome of this reaction, resulting in a Prins-type reaction cascade initiated by a p-quinone methide intermediate, and leading to an unexpected cycloadduct. The corresponding 20-deoxy precursor, as suggested for the naturally occurring IMDA precursor smoothly yields the desired IMDA product as a mixture of two endo products. These results support the hypothesis that nature probably uses an intramolecular Diels–Alder cycloaddition to generate the bicyclic core of the elansolids starting from a 20-deoxygenated precursor.
Keywords
- Biomimetic synthesis, Cyclization, Cycloaddition, Diels–Alder reaction, Natural products, Prins reaction
ASJC Scopus subject areas
- Chemistry(all)
- Physical and Theoretical Chemistry
- Chemistry(all)
- Organic Chemistry
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In: European Journal of Organic Chemistry, Vol. 2017, No. 37, 28.08.2017, p. 5582-5591.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Synthetic Studies Probing Elansolid Biosynthesis
T2 - A para-Quinone-Methide-Triggered Intramolecular Diels–Alder Reaction
AU - Wang, Liangliang
AU - Candito, David
AU - Dräger, Gerald
AU - Kirschning, Andreas
N1 - Funding information: The work was funded in part by the Deutsche Forschungsge-meinschaft (Cluster of Excellence REBIRTH; “From Regenerative Biology to Reconstructive Therapy” EXC 62). D. C. thanks the Alexander-von-Humboldt Foundation for a postdoctoral scholarship.
PY - 2017/8/28
Y1 - 2017/8/28
N2 - The elansolids A1/A2 and B1–B3 are secondary metabolites formed by the gliding bacterium Chitinophaga sancti. They show antibacterial activity against Gram-positive bacteria. It has been proposed that the biosynthesis of the tetrahydroindane unit involves an intramolecular Diels–Alder cycloaddition (IMDA). To study the biosynthetic proposal, the influence of an oxygen functionality at C-20, the regiochemistry of the allylic alcohol precursor, and the nature of the phenol group were investigated. The oxygen functionality at C-20 has a profound effect on the outcome of this reaction, resulting in a Prins-type reaction cascade initiated by a p-quinone methide intermediate, and leading to an unexpected cycloadduct. The corresponding 20-deoxy precursor, as suggested for the naturally occurring IMDA precursor smoothly yields the desired IMDA product as a mixture of two endo products. These results support the hypothesis that nature probably uses an intramolecular Diels–Alder cycloaddition to generate the bicyclic core of the elansolids starting from a 20-deoxygenated precursor.
AB - The elansolids A1/A2 and B1–B3 are secondary metabolites formed by the gliding bacterium Chitinophaga sancti. They show antibacterial activity against Gram-positive bacteria. It has been proposed that the biosynthesis of the tetrahydroindane unit involves an intramolecular Diels–Alder cycloaddition (IMDA). To study the biosynthetic proposal, the influence of an oxygen functionality at C-20, the regiochemistry of the allylic alcohol precursor, and the nature of the phenol group were investigated. The oxygen functionality at C-20 has a profound effect on the outcome of this reaction, resulting in a Prins-type reaction cascade initiated by a p-quinone methide intermediate, and leading to an unexpected cycloadduct. The corresponding 20-deoxy precursor, as suggested for the naturally occurring IMDA precursor smoothly yields the desired IMDA product as a mixture of two endo products. These results support the hypothesis that nature probably uses an intramolecular Diels–Alder cycloaddition to generate the bicyclic core of the elansolids starting from a 20-deoxygenated precursor.
KW - Biomimetic synthesis
KW - Cyclization
KW - Cycloaddition
KW - Diels–Alder reaction
KW - Natural products
KW - Prins reaction
UR - http://www.scopus.com/inward/record.url?scp=85030750468&partnerID=8YFLogxK
U2 - 10.1002/ejoc.201701125
DO - 10.1002/ejoc.201701125
M3 - Article
AN - SCOPUS:85030750468
VL - 2017
SP - 5582
EP - 5591
JO - European Journal of Organic Chemistry
JF - European Journal of Organic Chemistry
SN - 1434-193X
IS - 37
ER -