Abstract
A one-pot methodology to synthesize metastable bicyclic 2,5-dihydrooxepines from cyclic 1,3-diketones and 1,4-dibromo-2-butenes through the retro-Claisen rearrangement of syn-2-vinylcyclopropyl diketone intermediates is reported. DFT calculations were performed to understand the reaction selectivity and mechanisms towards [1,3]- or [3,3]-sigmatropic rearrangements, highlighting the crucial influence of the temperature. The reaction was successfully applied to a short protecting group-free total synthesis of radulanin A, a natural 2,5-dihydrobenzoxepine. Moreover, the strong herbicidal potential of this natural product is demonstrated for the first time.
| Original language | English |
|---|---|
| Pages (from-to) | 8643-8648 |
| Number of pages | 6 |
| Journal | Chemistry - A European Journal |
| Volume | 25 |
| Issue number | 36 |
| DOIs | |
| Publication status | Published - 26 Jun 2019 |
Keywords
- 2,5-dihydrooxepines
- density functional calculations
- herbicides
- sigmatropic rearrangement
- total synthesis
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