Details
| Original language | English |
|---|---|
| Pages (from-to) | 7021-7029 |
| Number of pages | 9 |
| Journal | Journal of the American Chemical Society |
| Volume | 145 |
| Issue number | 12 |
| Early online date | 16 Mar 2023 |
| Publication status | Published - 29 Mar 2023 |
Abstract
The discovery of illisimonin A in 2017 extended the structural repertoire of the Illicium sesquiterpenoids─a class of natural products known for their high oxidation levels and neurotrophic properties─with a new carbon backbone combining the strained trans-pentalene and norbornane substructures. We report an asymmetric total synthesis of (−)-illisimonin A that traces its tricyclic carbon framework back to a spirocyclic precursor, generated by a tandem-Nazarov/ene cyclization. As crucial link between the spirocyclic key intermediate and illisimonin A, a novel approach for the synthesis of tricyclo[5.2.1.01,5]decanes via radical cyclization was explored. This approach was applied in a two-stage strategy consisting of Ti(III)-mediated cyclization and semipinacol rearrangement to access the natural product’s carbon backbone. These key steps were combined with carefully orchestrated C-H oxidations to establish the dense oxidation pattern.
ASJC Scopus subject areas
- Chemical Engineering(all)
- Catalysis
- Chemistry(all)
- General Chemistry
- Biochemistry, Genetics and Molecular Biology(all)
- Biochemistry
- Chemical Engineering(all)
- Colloid and Surface Chemistry
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In: Journal of the American Chemical Society, Vol. 145, No. 12, 29.03.2023, p. 7021-7029.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Asymmetric Total Synthesis of Illisimonin A
AU - Etling, Christoph
AU - Tedesco, Giada
AU - Di Marco, Anna
AU - Kalesse, Markus
N1 - Funding Information: We thank M. Rettstadt, D. Körtje, J. Fohrer, L. K. Müggenburg, and M. Bauer for detailed NMR analysis, A. Schulz and G. Dräger for mass spectra, G. Dräger for X-ray analysis, and P. Stolle for CD spectra. We thank T. Blodau for his good work during an internship with us and M. Alekseychuk, A. Eggert, Y. Linne, M. Saxarra, and B. Siekmeyer for proofreading. Special thanks are expressed to A. S. Burns, S. D. Rychnovsky, and P. Heretsch for helpful discussions.
PY - 2023/3/29
Y1 - 2023/3/29
N2 - The discovery of illisimonin A in 2017 extended the structural repertoire of the Illicium sesquiterpenoids─a class of natural products known for their high oxidation levels and neurotrophic properties─with a new carbon backbone combining the strained trans-pentalene and norbornane substructures. We report an asymmetric total synthesis of (−)-illisimonin A that traces its tricyclic carbon framework back to a spirocyclic precursor, generated by a tandem-Nazarov/ene cyclization. As crucial link between the spirocyclic key intermediate and illisimonin A, a novel approach for the synthesis of tricyclo[5.2.1.01,5]decanes via radical cyclization was explored. This approach was applied in a two-stage strategy consisting of Ti(III)-mediated cyclization and semipinacol rearrangement to access the natural product’s carbon backbone. These key steps were combined with carefully orchestrated C-H oxidations to establish the dense oxidation pattern.
AB - The discovery of illisimonin A in 2017 extended the structural repertoire of the Illicium sesquiterpenoids─a class of natural products known for their high oxidation levels and neurotrophic properties─with a new carbon backbone combining the strained trans-pentalene and norbornane substructures. We report an asymmetric total synthesis of (−)-illisimonin A that traces its tricyclic carbon framework back to a spirocyclic precursor, generated by a tandem-Nazarov/ene cyclization. As crucial link between the spirocyclic key intermediate and illisimonin A, a novel approach for the synthesis of tricyclo[5.2.1.01,5]decanes via radical cyclization was explored. This approach was applied in a two-stage strategy consisting of Ti(III)-mediated cyclization and semipinacol rearrangement to access the natural product’s carbon backbone. These key steps were combined with carefully orchestrated C-H oxidations to establish the dense oxidation pattern.
UR - http://www.scopus.com/inward/record.url?scp=85150377568&partnerID=8YFLogxK
U2 - 10.1021/jacs.3c01262
DO - 10.1021/jacs.3c01262
M3 - Article
C2 - 36926847
AN - SCOPUS:85150377568
VL - 145
SP - 7021
EP - 7029
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 12
ER -