Details
| Original language | English |
|---|---|
| Pages (from-to) | 5812-5816 |
| Number of pages | 5 |
| Journal | Organic letters |
| Volume | 24 |
| Issue number | 31 |
| Early online date | 1 Aug 2022 |
| Publication status | Published - 12 Aug 2022 |
Abstract
The first bioinspired, enantioselective, and protecting group free total synthesis of the antibacterial sesquiterpenoid (-)-antroalbocin A (1) has been achieved in 12 steps (5.4% overall yield) from dimedone. An organocatalytic Robinson annulation gave rapid access to the tricyclic enone (19) as starting material for the photochemical domino process of deconjugation and sigmatropic 1,3-acyl shift. Computational data of this process indicate that the 1,3-acyl shift benefits from the highly strained 1,3-enone 8. The transformation of 8 to its bridged isomer 5 is exergonic and, therefore, enables an increased conversion compared to unstrained substrates.
ASJC Scopus subject areas
- Biochemistry, Genetics and Molecular Biology(all)
- Biochemistry
- Chemistry(all)
- Physical and Theoretical Chemistry
- Chemistry(all)
- Organic Chemistry
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In: Organic letters, Vol. 24, No. 31, 12.08.2022, p. 5812-5816.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Total Synthesis of (-)-Antroalbocin A Enabled by a Strain Release-Controlled Photochemical 1,3-Acyl Shift
AU - Siekmeyer, Björn
AU - Lübken, Dennis
AU - Bajerke, Kevin
AU - Bernhardt, Bastian
AU - Schreiner, Peter R.
AU - Kalesse, Markus
PY - 2022/8/12
Y1 - 2022/8/12
N2 - The first bioinspired, enantioselective, and protecting group free total synthesis of the antibacterial sesquiterpenoid (-)-antroalbocin A (1) has been achieved in 12 steps (5.4% overall yield) from dimedone. An organocatalytic Robinson annulation gave rapid access to the tricyclic enone (19) as starting material for the photochemical domino process of deconjugation and sigmatropic 1,3-acyl shift. Computational data of this process indicate that the 1,3-acyl shift benefits from the highly strained 1,3-enone 8. The transformation of 8 to its bridged isomer 5 is exergonic and, therefore, enables an increased conversion compared to unstrained substrates.
AB - The first bioinspired, enantioselective, and protecting group free total synthesis of the antibacterial sesquiterpenoid (-)-antroalbocin A (1) has been achieved in 12 steps (5.4% overall yield) from dimedone. An organocatalytic Robinson annulation gave rapid access to the tricyclic enone (19) as starting material for the photochemical domino process of deconjugation and sigmatropic 1,3-acyl shift. Computational data of this process indicate that the 1,3-acyl shift benefits from the highly strained 1,3-enone 8. The transformation of 8 to its bridged isomer 5 is exergonic and, therefore, enables an increased conversion compared to unstrained substrates.
UR - http://www.scopus.com/inward/record.url?scp=85135999138&partnerID=8YFLogxK
U2 - 10.26434/chemrxiv-2021-3pd4x
DO - 10.26434/chemrxiv-2021-3pd4x
M3 - Article
C2 - 35912985
AN - SCOPUS:85135999138
VL - 24
SP - 5812
EP - 5816
JO - Organic letters
JF - Organic letters
SN - 1523-7060
IS - 31
ER -