Enantioselective Total Synthesis of (+)-Plumisclerinâ
A.
Angew Chem Int Ed Engl
; 57(40): 13313-13318, 2018 10 01.
Article
em En
| MEDLINE
| ID: mdl-30112791
ABSTRACT
The first and enantioselective total synthesis of (+)-plumisclerinâ
A, a novel unique complex cytotoxic marine diterpenoid, has been accomplished. Around the central cyclopentane anchorage, a sequential ring-formation protocol was adopted to generate the characteristic tricycle[4.3.1.01,5 ]decane and trans-fused dihyrdopyran moiety. Scalable enantioselective LaIII -catalyzed Michael reaction, palladium(0)-catalyzed carbonylation and SmI2 -mediated radical conjugate addition were successfully applied in the synthesis, affording multiple grams of the complex and rigid B/C/D-ring system having six continuous stereogenic centers and two all-carbon quaternary centers. The trans-fused dihyrdopyran moiety with an exo side-chain was furnished in final stage through sequential redox transformations from a lactone precursor, which overcome the largish steric strain of the dense multiring system. The reported total synthesis also confirms the absolute chemistries of natural (+)-plumisclerinâ
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Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Diterpenos
Idioma:
En
Ano de publicação:
2018
Tipo de documento:
Article