ol0c02930_si_001.pdf (3.21 MB)
Total Synthesis of (−)-Sigillin A: A Polychlorinated and Polyoxygenated Natural Product
journal contribution
posted on 2020-09-16, 14:07 authored by Yousuke Yamaoka, Takamori Nakayama, Shota Kawai, Kiyosei TakasuThe total synthesis
of (−)-sigillin A, a highly chlorinated
and oxygenated octahydroisocoumarin, is described herein. A hexahydroisocoumarin
skeleton was constructed from (R)-4-(trichloromethyl)oxetan-2-one
in seven steps. Its unique manganese oxidation provided an enone as
the key intermediate of sigillin A. Stereoselective installation of
two hydroxy groups and formation of gem-dichloroalkene
from the corresponding ketone led to the total synthesis of (−)-sigillin
A in a total of 16 steps.
