Total Synthesis of Beshanzuenone D and Its Epimers and Abiespiroside A

Org Lett. 2020 Nov 6;22(21):8561-8565. doi: 10.1021/acs.orglett.0c03157. Epub 2020 Oct 26.

Abstract

A unified and protecting-group-free six-step total synthesis of bisabolane-type sesquiterpenoid beshanzuenone D and its stereoisomers and abiespiroside A using S-(+)-carvone as a common chiral-pool building block is disclosed. This synthetic route features chemoselective allylic chlorination of carvone, Au(I)-catalyzed cycloisomerization induced construction of furan from homopropargylic diol, substrate-controlled selective hydroxylation using Davis-oxaziridine, and dye-sensitized photo-oxidation (through 1O2) of hydroxyalkyl tethered furan to access oxaspirolactone as key transformations. A comprehensive set of NMR data along with DFT calculations, ECD spectra, and optical rotation measurements of the synthesized beshanzuenone D and its epimers were obtained to confirm absolute configurations.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Catalysis
  • Chemistry Techniques, Synthetic
  • Sesquiterpenes / chemical synthesis*
  • Sesquiterpenes / chemistry*
  • Stereoisomerism

Substances

  • Sesquiterpenes