title: Electrophilic aromatic substitutions of aryltrifluoroborates with retention of the BF3- group: quantification of the activating and directing effects of the trifluoroborate group.
abstract: Kinetics and mechanisms of transition-metal free reactions of furyl, thienyl and indolyl trifluoroborates with benzhydrylium (Ar2CH(+)) and iminium (Me2N(+)═CHR) ions have been investigated. In contrast to common belief, substitutions at CH positions are often faster than ipso-substitutions of the BF3K group, because BF3K activates the position attached to boron by a factor of 10(3)-10(4) while adjacent CH positions are activated by factors of 10(5)-10(6). Several reactions that have previously been interpreted as ipso-substitutions actually proceed via initial substitution at a vicinal or remote CH position, followed by protodeborylation. If the proton released during electrophilic substitution at a CH position is trapped by a base, the BF3(-) group can be preserved. Remote reactions of heteroaryl trifluoroborates with iminium ions provide straightforward access to novel zwitterionic ammonium or iminium trifluoroborates, which have been characterized by single-crystal X-ray analyses.
authors.affiliation: Department Chemie, Ludwig-Maximilians- Universität München, Butenandtstr. 5-13 (Haus F), 81377 München, Germany.
authors.forename: Guillaume
authors.initials: G
authors.lastname: Berionni
authors.forename: Varvara
authors.initials: V
authors.lastname: Morozova
authors.forename: Maximilian
authors.initials: M
authors.lastname: Heininger
authors.forename: Peter
authors.initials: P
authors.lastname: Mayer
authors.forename: Paul
authors.initials: P
authors.lastname: Knochel
authors.forename: Herbert
authors.initials: H
authors.lastname: Mayr