title: Application of α-alkoxy bridgehead radical for coupling of oxygenated carbocycles.
abstract: A new coupling methodology for assembly of highly oxygenated carbocycles was developed. An α-alkoxy bridgehead radical was employed as the key reactive intermediate due to its potent reactivity, minimum steric interaction, and predestined stereochemical outcome. The radical of the trioxadamantane structure, generated from the O,Se-acetal, was reacted with electron-deficient cyclic olefins of various ring sizes. Intermolecular formation of sterically congested linkages between two tetrasubstituted carbons and application of the method to a three-component coupling were two significant achievements.
authors.affiliation: Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Tokyo 113-0033, Japan.
authors.forename: Daisuke
authors.initials: D
authors.lastname: Urabe
authors.forename: Hiroki
authors.initials: H
authors.lastname: Yamaguchi
authors.forename: Masayuki
authors.initials: M
authors.lastname: Inoue
mesh_terms: D018360:Crystallography, X-Ray; D003516:Cycloparaffins / Q000737:chemistry; D005609:Free Radicals / Q000138:chemical synthesis / Q000737:chemistry; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D009570:Nitriles / Q000138:chemical synthesis* / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D003516:Cycloparaffins; D005609:Free Radicals; D007659:Ketones; D009570:Nitriles; D010100:Oxygen