Enantioselective Total Synthesis of Berkeleyoneâ
A and Preaustinoids.
Angew Chem Int Ed Engl
; 60(27): 14869-14874, 2021 06 25.
Article
en En
| MEDLINE
| ID: mdl-33856105
ABSTRACT
Herein we report the first enantioselective total synthesis of 3,5-dimethylorsellinic acid-derived meroterpenoids (-)-berkeleyone A and its five congeners ((-)-preaustinoidsâ
A, A1, B, B1, and B2) in 12-15 steps, starting from commercially available 2,4,6-trihydroxybenzoic acid hydrate. Based upon the recognition of latent symmetry within D-ring, our convergent synthesis features two critical reactions 1)â
a symmetry-breaking, diastereoselective dearomative alkylation to assemble the entire carbon core, and 2)â
a Sc(OTf)3 -mediated sequential Krapcho dealkoxycarbonylation/carbonyl α-tert-alkylation to forge the intricate bicyclo[3.3.1]nonane framework. We also conducted our preliminary biomimetic investigations and uncovered a series of rearrangements (α-ketol, α-hydroxyl-ß-diketone, etc.) responsible for the biomimetic diversification of (-)-berkeleyoneâ
A into its five preaustinoid congeners.
Texto completo:
1
Colección:
01-internacional
Banco de datos:
MEDLINE
Idioma:
En
Revista:
Angew Chem Int Ed Engl
Año:
2021
Tipo del documento:
Article
País de afiliación:
China