Xu B,
Liu C,
Dai M.
*
Emory University, Atlanta, USA
Catalysis-Enabled 13-Step Total Synthesis of (–)-Peyssonnoside A.
J. Am. Chem. Soc. 2022;
144: 19700-19703
DOI:
10.1021/jacs.2c09919
Key words
(–)-peyssonnoside A - diterpene glycoside - marine natural product - antimicrobial
- dearomative cyclization - HAT-initiated cyclization - Wittig reaction - Mukaiyama
hydration
Significance
Dai and co-workers present a concise synthesis of (–)-peyssonnoside A, a sulfated
diterpene glycoside which was isolated in 2019 from the red alga Peyssonnelia sp. (–)-Peyssonnoside A stands out through its sterically encumbered, pentasubstituted
cyclopropane ring which represents a key synthetic challenge.
Comment
Enantioselective conjugate addition to enone A and subsequent enolate trapping with propargyl bromide D furnished ketone E. Palladium-catalyzed hydroarylation and functional group interconversion to phenol
H set the stage for dearomative cyclization to dienone J. HAT-initiated cyclization secured the encumbered cyclopropane K and paved the way to (–)-peyssonnoside A.
