Collective Syntheses of Icetexane Natural Products Based on Biogenetic Hypotheses

Article abstract of DOI:10.1002/chem.201603932

A divergent synthesis of 10 icetexane natural products based on a proposed biogenetic cationic ring expansion of a reduced carnosic acid derivative is described. Of these icetexanes, (+)-salvicanol, (?)-cyclocoulterone, (?)-coulterone, (?)-obtusinone D, and (?)-obtusinone E have been synthesized for the first time. In addition, the hypothesis for the non-enzymatic biogenesis of benzo[1,3]dioxole natural products has been experimentally investigated. Additional experimental evidence for the abiotic formation of the methylenedioxy unit is provided, as photolysis of the quinone (+)-komaroviquinone resulted in the formation of the [1,3]dioxole-containing natural product (?)-cyclocoulterone and (+)-komarovispirone.