title: Constructing quaternary stereogenic centers using tertiary organocuprates and tertiary radicals. Total synthesis of trans-clerodane natural products.
abstract: A new concise construction of trans-clerodane diterpenoids is reported in which oxacyclic and trans-hydronaphthalene fragments are coupled, and the critical C9-quaternary carbon stereocenter formed stereoselectively, by 1,6-addition of a tertiary cuprate or a tertiary carbon radical to β-vinylbutenolide. This strategy is specifically illustrated by total syntheses of (-)-solidagolactone (4), (-)-16-hydroxycleroda-3,13-dien-15,16-olide (5, PL3), and (-)-annonene (6).
authors.affiliation: Department of Chemistry, University of California, Irvine , 1102 Natural Sciences II, Irvine, California 92697-2025, United States.
authors.forename: Daniel S
authors.initials: DS
authors.lastname: Müller
authors.forename: Nicholas L
authors.initials: NL
authors.lastname: Untiedt
authors.forename: André P
authors.initials: AP
authors.lastname: Dieskau
authors.forename: Gregory L
authors.initials: GL
authors.lastname: Lackner
authors.forename: Larry E
authors.initials: LE
authors.lastname: Overman
mesh_terms: D001688:Biological Products / Q000138:chemical synthesis* / Q000737:chemistry*; D060326:Chemistry Techniques, Synthetic; D003300:Copper / Q000737:chemistry*; D045785:Diterpenes, Clerodane / Q000138:chemical synthesis* / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D001688:Biological Products; D045785:Diterpenes, Clerodane; D005609:Free Radicals; D003300:Copper