title: Copper-catalyzed cyanomethylation of allylic alcohols with concomitant 1,2-aryl migration: efficient synthesis of functionalized ketones containing an α-quaternary center.
abstract: A copper-catalyzed alkylation of allylic alcohols by alkyl nitriles with concomitant 1,2-aryl migration was developed. Formation of the alkyl nitrile radical was followed by its intermolecular addition to alkenes and the migration of a vicinal aryl group with the concomitant generation of a carbonyl functionality to complete the domino sequence. Mechanistic studies suggested that 1,2-aryl migration proceeded through a radical pathway (neophyl rearrangement). The protocol provided an efficient route to functionalized ketones containing an α-quaternary center.
authors.affiliation: Laboratory of Synthesis and Natural Products, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL-SB-ISIC-LSPN, BCH 5304, 1015 Lausanne (Switzerland) http://lspn.epfl.ch.
authors.forename: Ala
authors.initials: A
authors.lastname: Bunescu
authors.forename: Qian
authors.initials: Q
authors.lastname: Wang
authors.forename: Jieping
authors.initials: J
authors.lastname: Zhu
keywords: alkyl nitriles; allylic alcohols; copper triflate; ketones; neophyl rearrangement