Copper‐Catalyzed Cyanomethylation of Allylic Alcohols with Concomitant 1,2‐Aryl Migration: Efficient Synthesis of Functionalized Ketones Containing an α‐Quaternary Center |
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| Authors: | Dr. Ala Bunescu Dr. Qian Wang Prof. Dr. Jieping Zhu |
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| 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 |
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| 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. |
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| Keywords: | alkyl nitriles allylic alcohols copper triflate ketones neophyl rearrangement |
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