Multiple chirality transfers in the enantioselective synthesis of 11-O-debenzoyltashironin. Chiroptical analysis of the key cascade.
The mechanism of the cascade oxidative dearomatization-transannular Diels Alder was investigated in the context of an asymmetric route to (-)-11-O-debenzoyltashironin. Although the oxidative dearomatization provides two acetal intermediates, the transannular Diels-Alder proceeds spontaneously from only one of the acetal isomers. Access to enantioenriched tetracyclic adduct was gained through the use of optically active allene.
Polara
Alessandra
A
Department of Chemistry, Columbia University, 3000 Broadway, New York, NY 10027, USA.
Cook
Silas P
SP
Danishefsky
Samuel J
SJ