Premium
Expanding the Balz–Schiemann Reaction: Organotrifluoroborates Serve as Competent Sources of Fluoride Ion for Fluoro‐Dediazoniation
Author(s) -
Mohy El Dine Tharwat,
Sadek Omar,
Gras Emmanuel,
Perrin David M.
Publication year - 2018
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.201803575
Subject(s) - fluoride , chemistry , salt (chemistry) , aryl , steric effects , fluorine , combinatorial chemistry , organic chemistry , inorganic chemistry , alkyl
The Balz–Schiemann reaction endures as a method for the preparation of (hetero)aryl fluorides yet is eschewed due to the need for harsh conditions or high temperatures along with the need to isolate potentially explosive diazonium salts. In a departure from these conditions, we show that various organotrifluoroborates (RBF 3 − s) may serve as fluoride ion sources for solution‐phase fluoro‐dediazoniation in organic solvents under mild conditions. This methodology was successfully extended to a one‐pot process obviating aryl diazonium salt isolation. Sterically hindered (hetero)anilines are fluorinated under unprecedentedly mild conditions in good‐to‐excellent yields. Taken together, this work expands the repertoire of RBF 3 − s to act as fluorine ion sources in an update to the classic Balz–Schiemann reaction.