Copper-Catalyzed Cyanomethylation of Allylic Alcohols with Concomitant 1,2-Aryl Migration: Efficient Synthesis of Functionalized Ketones Containing an α-Quaternary Center

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 a-quaternary center.


Published in:
Angewandte Chemie International Edition, 54, 10, 3132-3135
Year:
2015
Publisher:
Weinheim, Wiley-Blackwell
ISSN:
1433-7851
Keywords:
Laboratories:




 Record created 2015-02-25, last modified 2018-09-13


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