Bioinspired Asymmetric Total Synthesis of Emerionesâ
A-C.
Angew Chem Int Ed Engl
; 61(32): e202205878, 2022 08 08.
Article
em En
| MEDLINE
| ID: mdl-35670768
ABSTRACT
We report asymmetric bioinspired total syntheses of the fungal metabolites emerionesâ
A-C via stereoselective oxidations of two bicyclo[4.2.0]octadiene diastereomers. The central bicyclic scaffolds are prepared in an 8π/6π electrocyclization cascade of a stereodefined pentaene, which contains the fully assembled side chains of the emeriones. The anti-aldol side chain is made using a Paterson-aldol addition, and the epoxide of the dioxabicyclo[3.1.0]hexane side chain via ring-closure onto an oxidized acetal. Our work has enabled the structural revision of emerioneâ
C, and resulted in the synthesis of a "missing" family member, which we call emerioneâ
D. DFT calculations identified two methyl groups that govern torquoselectivity in the 8π/6π cascade.
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Base de dados:
MEDLINE
Assunto principal:
Estereoisomerismo
Idioma:
En
Ano de publicação:
2022
Tipo de documento:
Article