title: Dramatic effect of solvent hydrogen bond basicity on the regiochemistry of S(N)Ar reactions of electron-deficient polyfluoroarenes.
abstract: It was found that solvent hydrogen bond basicity (SHBB) significantly affects the regiochemistry of the S(N)Ar reaction between secondary amines and activated polyfluoroarenes. A plausible mechanism involving a six-membered transition state is invoked for the formation of an ortho-substituted isomer, which is likely organized by a hydrogen bond. Evidence for this hypothesis is presented, and a regioselective amination reaction of activated polyfluoroarenes has been developed.
authors.affiliation: Chemical Sciences, Wyeth Research, 401 North Middletown Road, Pearl River, New York 10965, USA. wangx4@wyeth.com
authors.forename: Xiaolun
authors.initials: X
authors.lastname: Wang
authors.forename: Edward J
authors.initials: EJ
authors.lastname: Salaski
authors.forename: Dan M
authors.initials: DM
authors.lastname: Berger
authors.forename: Dennis
authors.initials: D
authors.lastname: Powell
mesh_terms: D006845:Hydrocarbons, Fluorinated / Q000138:chemical synthesis / Q000737:chemistry*; D006860:Hydrogen Bonding; D015394:Molecular Structure; D012997:Solvents / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D006845:Hydrocarbons, Fluorinated; D012997:Solvents