Asymmetric [3,3]-Sigmatropic Rearrangement of Sulfoniums for the Synthesis of Quaternary Center-Containing Polycyclic Molecules: Application to the Total Synthesis of Myrmenaphthol A

01 November 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


The asymmetric total synthesis of myrmenaphthol A, a natural product isolated from a Hawaiian sponge of the genus myrmekioderma, has been achieved in 12 steps. The key transformation of this synthesis is a gold-catalyzed [3,3]-sigmatropic rearrangement of sulfonium, starting from a chiral sulfoxide substrate and propargyl silane. The development of the methodology included the synthesis of benz[e]inden-2-one derivatives with quaternary centers (51-78% yield, 90-99% ee).


Asymmetric synthesis
Sigmatropic rearrangement
Quaternary center
Myrmenaphthol A


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