Premium
Thiourea‐Catalyzed C−F Bond Activation: Amination of Benzylic Fluorides
Author(s) -
Houle Camille,
Savoie Paul R.,
Davies Clotilde,
Jardel Damien,
Champagne Pier Alexandre,
Bibal Brigitte,
Paquin JeanFrançois
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202001905
Subject(s) - amination , thiourea , catalysis , chemistry , nucleophile , fluorine , fluoride , substrate (aquarium) , scavenger , activation energy , medicinal chemistry , organic chemistry , radical , inorganic chemistry , oceanography , geology
We describe the first thiourea‐catalyzed C−F bond activation. The use of a thiourea catalyst and Ti(O i Pr) 4 as a fluoride scavenger allows the amination of benzylic fluorides to proceed in moderate to excellent yields. Preliminary results with S‐ and O‐based nucleophiles are also presented. DFT calculations reveal the importance of hydrogen bonds between the catalyst and the fluorine atom of the substrate to lower the activation energy during the transition state.