posted on 2024-01-18, 20:02authored byXin Wang, Mengjiao Zhang, Xiaolei Liu, Mingliang Lou, Gen Li, Xiangbing Qi
Skeleton rearrangement could rapidly
transfer simple molecules
to complex structures and has significant potential in the total synthesis
of natural products. We developed a one-pot reaction cascade of double
oxidative rearrangement of furan and indole followed by a nucleophilic
cyclization that was successfully applied for the formal synthesis
of rhynchophylline/isorhynchophylline and the first total synthesis
of (±)-7(R)-geissoschizol oxindole/(±)-7(S)-geissoschizol oxindole. In addition, the geissoschizol
oxindoles were revised to their C3 epimers, and the mechanism for
the reversed stereochemistry through the retro-Mannich/Mannich cascade
was proposed and supported by density functional theory calculations.