1.
Angew Chem Int Ed Engl
; 57(4): 947-951, 2018 01 22.
Artigo
em Inglês
| MEDLINE
| ID: mdl-29115009
RESUMO
(-)-Daphnilongeraninâ B and (-)-daphenylline are two hexacyclic Daphniphyllum alkaloids, each containing a complex cagelike backbone. Described herein are the first asymmetric total synthesis of (-)-daphnilongeraninâ B and a bioinspired synthesis of (-)-daphenylline with an unusual Eâ ring embedded in a cagelike framework. The key features include an intermolecular [3+2] cycloaddition, a late-stage aldol cyclization to install the Fâ ring of daphnilongeraninâ B, and a bioinspired cationic rearrangement leading to the tetrasubstituted benzene ring of daphenylline.