Allylic amination and carbon–carbon double bond transposition catalyzed by cobalt(II) azodioxide complexes

Results in Chemistry

W. Christopher Boyd¹  Lakshmi Balaraman²  Drew M. Kingery²  Kylin A. Emhoff²  Ahmed M.H. Salem² 

[1] Corresponding author.;Department of Chemistry, Cleveland State University, 2121 Euclid Avenue, Cleveland, OH 44114, United States;

关键词: Cobalt;    Azodioxide;    Amination;    Allylic alkenes;    Catalysis;   

DOI  :  

来源: DOAJ

【 摘 要 】

The unusual cobalt(II) diphenylazodioxide complex salts [Co(az)4](PF6)2 and [Co(bpy)(az)2](PF6)2 have been shown to catalyze the allylic amination/C–C double bond transposition reaction of 2-methyl-2-pentene with PhNHOH, with a turnover number of about 4. The mechanism is proposed to involve a nitroso-ene-like transfer of a PhNO moiety from the azodioxide ligand to the alkene, followed by reduction of the organic product to yield a cobalt(III) intermediate, which is itself reduced back to cobalt(II) by PhNHOH, regenerating PhNO. Hetero-Diels-Alder trapping experiments suggest that an “off-metal” mechanism, in which PhNO is released from the cobalt complexes and reacts with the alkenes, is operative, in contrast to an “on-metal” mechanism observed by Nicholas and coworkers for [Fe(az)3](FeCl4)2.

【 授权许可】

Unknown