Total Synthesis of (–)-Peyssonnoside A

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.

Publication History

Article published online:
17 January 2023