Total Synthesis of 6-Deoxydihydrokalafungin, a Key Biosynthetic Precursor of Actinorhodin, and Its Epimer
In this article, we report the total synthesis of 6-deoxydihydrokalafungin (DDHK), a key biosynthetic intermediate of a dimeric benzoisochromanequinone antibiotic, actinorhodin (ACT), and its epimer, <i>epi</i>-DDHK. Tricyclic hemiacetal with 3-siloxyethyl group was subjected to Et<su...
Guardado en:
| Autores principales: | , , , , , , |
|---|---|
| Formato: | article |
| Lenguaje: | EN |
| Publicado: |
MDPI AG
2021
|
| Materias: | |
| Acceso en línea: | https://doaj.org/article/95b1e4ae72584a8a99ccff564079d48e |
| Etiquetas: |
Agregar Etiqueta
Sin Etiquetas, Sea el primero en etiquetar este registro!
|
| Sumario: | In this article, we report the total synthesis of 6-deoxydihydrokalafungin (DDHK), a key biosynthetic intermediate of a dimeric benzoisochromanequinone antibiotic, actinorhodin (ACT), and its epimer, <i>epi</i>-DDHK. Tricyclic hemiacetal with 3-siloxyethyl group was subjected to Et<sub>3</sub>SiH reduction to establish the 1,3-<i>cis</i> stereochemistry in the benzoisochromane, and a subsequent oxidation/deprotection sequence then afforded <i>epi</i>-DDHK. A bicyclic acetal was subjected to AlH<sub>3</sub> reduction to deliver the desired 1,3-<i>trans</i> isomer in an approximately 3:1 ratio, which was subjected to a similar sequence to that used for the 1,3-<i>cis</i> isomer that successfully afforded DDHK. A semisynthetic approach from (<i>S</i>)-DNPA, an isolable biosynthetic precursor of ACT, was also examined to afford DDHK and its epimer, which are identical to the synthetic products. |
|---|