Fluorinated Solvents for Chemoselective Oxidations: A Strategy toward Synthetic Ideality in Natural Product Synthesis

Late-stage catalytic oxidations of complex natural products have been shown to exhibit dramatically improved chemoselectivity through the crucial use of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), even in the presence of oxidatively sensitive groups, such as hydroxyls and diols. This strategy reduced the need for protecting groups, effectively mimicking enzymatic pathways, and substantially enhancing synthetic ideality in the preparation of ent-beyerane and ent-kaurane metabolites.