title: Total synthesis of the Lycopodium alkaloid serratezomine A using free radical-mediated vinyl amination to prepare a β-stannyl enamine linchpin.
abstract: Serratezomine A is a member of the structurally diverse class of compounds known as the Lycopodium alkaloids. The key supporting studies and successful total synthesis of serratezomine A are described in this account. Significant features of the synthesis include the first application of free radical mediated vinyl amination and Hwu's oxidative allylation in a total synthesis and an intramolecular lactonization via a transannular S(N)i reaction. Minimal use of protecting groups and the highly diastereoselective formation of a hindered, quaternary stereocenter using an umpolung allylation are also highlights from a strategy perspective. Observation of quaternary carbon epimerization via a retro-Mannich/Mannich sequence highlights the additional challenge presented by the axial alcohol at C8 in serratezomine A.
authors.affiliation: Department of Chemistry & Vanderbilt Institute of Chemical Biology, Vanderbilt University, Nashville, Tennessee 37235-1822, USA.
authors.forename: Julie A
authors.initials: JA
authors.lastname: Pigza
authors.forename: Jeong-Seok
authors.initials: JS
authors.lastname: Han
authors.forename: Aroop
authors.initials: A
authors.lastname: Chandra
authors.forename: Daniel
authors.initials: D
authors.lastname: Mutnick
authors.forename: Maren
authors.initials: M
authors.lastname: Pink
authors.forename: Jeffrey N
authors.initials: JN
authors.lastname: Johnston
mesh_terms: D000470:Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D000586:Amination; D005609:Free Radicals / Q000737:chemistry*; D007212:Indolizines / Q000138:chemical synthesis* / Q000737:chemistry; D032502:Lycopodium / Q000737:chemistry*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D013237:Stereoisomerism
chemical_list: D000470:Alkaloids; D005609:Free Radicals; D007212:Indolizines; C415194:serratezomine A