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Copper‐Catalyzed Cyanomethylation of Allylic Alcohols with Concomitant 1,2‐Aryl Migration: Efficient Synthesis of Functionalized Ketones Containing an α‐Quaternary Center
Author(s) -
Bunescu Ala,
Wang Qian,
Zhu Jieping
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201411657
Subject(s) - aryl , chemistry , allylic rearrangement , alkyl , vicinal , catalysis , organic chemistry , medicinal chemistry , combinatorial chemistry
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.