2019 Volume 77 Issue 1 Pages 13-25
Described herein are the synthetic strategies toward polyketide-derived polycyclic compounds decorated by post-functionalizations. The approaches are based on two key reactions, (1) annulation via benzonitrile oxide, and (2) benzoin cyclization, providing a linear tricarbocyclic intermediate with an angular hydroxy group. Also described are the stereocontrolled introduction of angular substituents via pinacol-type 1,2-shift and N-methylation-hydroxylation to pave the way to advanced intermediates. The synthetic utility of the approach has been highlighted by successful total syntheses of some structurally complex, polycyclic natural products.
