title: Remote Hydroxylation through Radical Translocation and Polar Crossover.
abstract: Mild conditions are reported for the hydroxylation of aliphatic C-H bonds through radical translocation, oxidation to carbocation, and nucleophilic trapping with H2O. This remote functionalization employs fac-[Ir(ppy)3] together with Tz(o) sulfonate esters and sulfonamides to facilitate the site-selective replacement of relatively inert C-H bonds with the more synthetically useful C-OH group. The hydroxylation of a range of substrates and the methoxylation of two substrates through 1,6- and 1,7-hydrogen-atom transfer are demonstrated. In addition, a synthesis of the antidepressant fluoxetine using remote hydroxylation as a key step is presented.
authors.affiliation: Department of Chemistry, Louisiana State University, 232 Choppin Hall, Baton Rouge, LA 70803 (USA).
authors.forename: Kyle A
authors.initials: KA
authors.lastname: Hollister
authors.affiliation: Department of Chemistry, Louisiana State University, 232 Choppin Hall, Baton Rouge, LA 70803 (USA).
authors.forename: Elizabeth S
authors.initials: ES
authors.lastname: Conner
authors.affiliation: Department of Chemistry, Louisiana State University, 232 Choppin Hall, Baton Rouge, LA 70803 (USA).
authors.forename: Mark L
authors.initials: ML
authors.lastname: Spell
authors.affiliation: Department of Chemistry, Louisiana State University, 232 Choppin Hall, Baton Rouge, LA 70803 (USA).
authors.forename: Kristina
authors.initials: K
authors.lastname: Deveaux
authors.affiliation: Department of Chemistry, Louisiana State University, 232 Choppin Hall, Baton Rouge, LA 70803 (USA).
authors.forename: Léa
authors.initials: L
authors.lastname: Maneval
authors.affiliation: Department of Chemistry, Louisiana State University, 232 Choppin Hall, Baton Rouge, LA 70803 (USA).
authors.forename: Michael W
authors.initials: MW
authors.lastname: Beal
authors.affiliation: Department of Chemistry, Louisiana State University, 232 Choppin Hall, Baton Rouge, LA 70803 (USA). jragains@lsu.edu.
authors.forename: Justin R
authors.initials: JR
authors.lastname: Ragains
mesh_terms: D000438:Alcohols / Q000138:chemical synthesis; D002244:Carbon / Q000737:chemistry; D002384:Catalysis; D005473:Fluoxetine / Q000138:chemical synthesis; D006838:Hydrocarbons / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry; D006900:Hydroxylation; D007495:Iridium / Q000737:chemistry; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D013449:Sulfonamides / Q000737:chemistry; D013451:Sulfonic Acids / Q000737:chemistry; D014867:Water / Q000737:chemistry*
chemical_list: D000438:Alcohols; D006838:Hydrocarbons; D013449:Sulfonamides; D013451:Sulfonic Acids; D005473:Fluoxetine; D014867:Water; D007495:Iridium; D002244:Carbon; D006859:Hydrogen; D010100:Oxygen
keywords: CH functionalization; hydroxylation; redox catalysis; remote functionalization; synthetic methods