title: Synthesis of Neurotrophic Seco-prezizaane Sesquiterpenes (1R,10S)-2-Oxo-3,4-dehydroneomajucin, (2S)-Hydroxy-3,4-dehydroneomajucin, and (-)-Jiadifenin.
abstract: An asymmetric approach to the synthesis of neurotrophic seco-prezizaane sesquiterpenes is described that is based on the strategic application of a hydroxyl-directed metallacycle-mediated [2 + 2 + 2] annulation and an intramolecular radical cyclization cascade. Targets prepared are among the most potent members of the natural product class and include (1R,10S)-2-oxo-3,4-dehydroneomajucin, (2S)-hydroxy-3,4-dehydroneomajucin, and (-)-jiadifenin. In addition to representing the first application of the alkoxide-directed metallacycle-mediated hydrindane-forming annulation reaction in natural product synthesis and the first total synthesis of (2S)-hydroxy-3,4-dehydroneomajucin, these pursuits have resulted in the elucidation of a complex radical cascade process for installation of the C5 quaternary center common to the natural product class.
authors.affiliation: Department of Chemistry, Burke Laboratory, Dartmouth College , Hanover, New Hampshire 03755, United States.
authors.forename: Xiayun
authors.initials: X
authors.lastname: Cheng
authors.affiliation: Department of Chemistry, Burke Laboratory, Dartmouth College , Hanover, New Hampshire 03755, United States.
authors.forename: Glenn C
authors.initials: GC
authors.lastname: Micalizio
mesh_terms: D015394:Molecular Structure; D012717:Sesquiterpenes / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D012717:Sesquiterpenes