Details
| Original language | English |
|---|---|
| Pages (from-to) | 104-108 |
| Number of pages | 5 |
| Journal | Journal of the American Chemical Society |
| Volume | 142 |
| Issue number | 1 |
| Early online date | 24 Dec 2019 |
| Publication status | Published - 8 Jan 2020 |
| Externally published | Yes |
Abstract
A switchable radical framework reconstruction approach to structurally unique 13(14 → 8),14(8 → 7)diabeo-steroid swinhoeisterol A was developed. The conversion of an ergostane skeleton proceeded through the intermediacy of a 13(14 → 8)abeo-framework as present in the dankasterone and periconiastone family of natural products and features a β scission of a 14-alkoxy radical with concomitant generation of the C8-C13 bond. From this intermediate, and dependent on the conditions employed, the cascade continues with a Dowd-Beckwith rearrangement and leads to the formation of the 13(14 → 8),14(8 → 7)diabeo-framework of the swinhoeisterol class of natural products. The synthesis of these frameworks then allowed for efficient access to swinhoeisterol A (1), dankasterone A (Δ 4-2), dankasterone B (2), and periconiastone A (3).
ASJC Scopus subject areas
- Chemical Engineering(all)
- Catalysis
- Chemistry(all)
- 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. 142, No. 1, 08.01.2020, p. 104-108.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Synthesis of Swinhoeisterol A, Dankasterone A and B, and Periconiastone A by Radical Framework Reconstruction
AU - Duecker, Fenja L.
AU - Heinze, Robert C.
AU - Heretsch, Philipp
N1 - Funding Information: Financial support for this work was provided by Deutsche Forschungsgemeinschaft (Grant No. HE 7133/7-1), the Boehringer Ingelheim Stiftung (exploration grant to P.H.), and Studienstiftung des Deutschen Volkes (Ph.D. scholarship to R.C.H.). We acknowledge the assistance of the Core Facility BioSupraMol supported by the DFG. We are grateful to Mira Mueller for experimental assistance, to Christiane Groneberg for HPLC separations, and to Prof. Dr. Dieter Lentz for X-ray crystallographic analyses (Freie Universität Berlin).
PY - 2020/1/8
Y1 - 2020/1/8
N2 - A switchable radical framework reconstruction approach to structurally unique 13(14 → 8),14(8 → 7)diabeo-steroid swinhoeisterol A was developed. The conversion of an ergostane skeleton proceeded through the intermediacy of a 13(14 → 8)abeo-framework as present in the dankasterone and periconiastone family of natural products and features a β scission of a 14-alkoxy radical with concomitant generation of the C8-C13 bond. From this intermediate, and dependent on the conditions employed, the cascade continues with a Dowd-Beckwith rearrangement and leads to the formation of the 13(14 → 8),14(8 → 7)diabeo-framework of the swinhoeisterol class of natural products. The synthesis of these frameworks then allowed for efficient access to swinhoeisterol A (1), dankasterone A (Δ 4-2), dankasterone B (2), and periconiastone A (3).
AB - A switchable radical framework reconstruction approach to structurally unique 13(14 → 8),14(8 → 7)diabeo-steroid swinhoeisterol A was developed. The conversion of an ergostane skeleton proceeded through the intermediacy of a 13(14 → 8)abeo-framework as present in the dankasterone and periconiastone family of natural products and features a β scission of a 14-alkoxy radical with concomitant generation of the C8-C13 bond. From this intermediate, and dependent on the conditions employed, the cascade continues with a Dowd-Beckwith rearrangement and leads to the formation of the 13(14 → 8),14(8 → 7)diabeo-framework of the swinhoeisterol class of natural products. The synthesis of these frameworks then allowed for efficient access to swinhoeisterol A (1), dankasterone A (Δ 4-2), dankasterone B (2), and periconiastone A (3).
UR - http://www.scopus.com/inward/record.url?scp=85077676480&partnerID=8YFLogxK
U2 - 10.1021/jacs.9b12899
DO - 10.1021/jacs.9b12899
M3 - Article
VL - 142
SP - 104
EP - 108
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 1
ER -