Dramatic effect of solvent hydrogen bond basicity on the regiochemistry of S(N)Ar reactions of electron-deficient polyfluoroarenes.
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.
Wang
Xiaolun
X
Chemical Sciences, Wyeth Research, 401 North Middletown Road, Pearl River, New York 10965, USA. wangx4@wyeth.com
Salaski
Edward J
EJ
Berger
Dan M
DM
Powell
Dennis
D
D006845:Hydrocarbons, Fluorinated / Q000138:chemical synthesis / Q000737:chemistry*; D006860:Hydrogen Bonding; D015394:Molecular Structure; D012997:Solvents / Q000737:chemistry; D013237:Stereoisomerism
D006845:Hydrocarbons, Fluorinated; D012997:Solvents