Total Synthesis of Pallamolides A-E.
Angew Chem Int Ed Engl
; 63(20): e202319127, 2024 May 13.
Article
em En
| MEDLINE
| ID: mdl-38504637
ABSTRACT
We have achieved the first total synthesis of pallamolides A-E. Of these compounds, pallamolides B-E possess intriguing tetracyclic skeletons with novel intramolecular transesterifications. Key transformations include highly diastereoselective sequential Michael addition reactions to construct the bicyclo[2.2.2]octane core with the simultaneous generation of two quaternary carbon centers, a one-pot SmI2-mediated intramolecular ketyl-enoate cyclization/ketone reduction to generate the key oxabicyclo[3.3.1]nonane moiety, and an acid-mediated deprotection/oxa-Michael addition/ß-hydroxy elimination cascade sequence to assemble the tetracyclic pallamolide skeleton. Kinetic resolution of ketone 14 through Corey-Bakshi-Shibata reduction enabled the asymmetric synthesis of pallamolides A-E.
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1
Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
Angew Chem Int Ed Engl
Ano de publicação:
2024
Tipo de documento:
Article
País de publicação:
Alemanha