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Barroso, Santiago; Lemaire, Sébastien; Farina, Vittorio; Steib, Andreas K.; Blanc, Romain; Knochel, Paul (2016): Cine Substitution with Arylzinc Reagents: Scope and Mechanistic Studies. In: Journal of Organic Chemistry, Vol. 81, No. 7: pp. 2804-2816
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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.