title: Cine Substitution with Arylzinc Reagents: Scope and Mechanistic Studies.
abstract: The unexpected ability of arylzinc reagents bearing electron-donating substituents to react in a Friedel-Crafts fashion (cine) with electrophiles like perpivaloylated glucoside bromide and benzhydryl bromides in competition with organometallic coupling (ipso) is shown. The stereoelectronic factors required to promote the cine reactivity versus the classical ipso, and the mechanism of this alternative pathway, have been investigated. The Wheland intermediate is deprotonated intramolecularly in a 1,2-shift but also in a longer-range shift, leaving in this case the C-Zn untouched. In the latter case, it is possible to take advantage of this result for further functionalization.
authors.affiliation: Pharmaceutical Development and Manufacturing Sciences, Janssen Pharmaceutica , Turnhoutseweg 30, 2340 Beerse, Belgium.
authors.forename: Santiago
authors.initials: S
authors.lastname: Barroso
authors.affiliation: Pharmaceutical Development and Manufacturing Sciences, Janssen Pharmaceutica , Turnhoutseweg 30, 2340 Beerse, Belgium.
authors.forename: Sébastien
authors.initials: S
authors.lastname: Lemaire
authors.affiliation: Pharmaceutical Development and Manufacturing Sciences, Janssen Pharmaceutica , Turnhoutseweg 30, 2340 Beerse, Belgium.
authors.forename: Vittorio
authors.initials: V
authors.lastname: Farina
authors.affiliation: Department of Chemistry and Biochemistry, Ludwig-Maximilians University of München , Butenandtstrasse 5-12, Haus F, 81377 München, Germany.
authors.forename: Andreas K
authors.initials: AK
authors.lastname: Steib
authors.affiliation: Department of Chemistry and Biochemistry, Ludwig-Maximilians University of München , Butenandtstrasse 5-12, Haus F, 81377 München, Germany.
authors.forename: Romain
authors.initials: R
authors.lastname: Blanc
authors.affiliation: Department of Chemistry and Biochemistry, Ludwig-Maximilians University of München , Butenandtstrasse 5-12, Haus F, 81377 München, Germany.
authors.forename: Paul
authors.initials: P
authors.lastname: Knochel