Cyanthiwigin Natural Product Core as a Complex Molecular Scaffold for Comparative Late-Stage C-H Functionalization Studies

The desire for maximally efficient transformations in complex molecule synthesis has contributed to a surge of interest in C-H functionalization methods development in recent years. In contrast to the steady stream of methodological reports, however, there are noticeably fewer studies comparing the efficacies of different C-H functionalization protocols on a single structurally intricate substrate. Recognizing the importance of heteroatom incorporation in complex molecule synthesis, this report discloses a comparative examination of diverse strategies for C-O, C-N, and C-X bond formation through late-stage C-H oxidation of the tricyclic cyanthiwigin natural product core. Methods for allylic C-H acetoxylation, tertiary C-H hydroxylation, tertiary C-H amination, tertiary C-H azidation, and secondary C-H halogenation are explored. These efforts highlight the robustness and selectivities of many well-established protocols for C-H oxidation when applied to a complex molecular framework, and the findings are relevant to chemists aiming to employ such strategies in the context of chemical synthesis.