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Issue 5, 2015
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Development of zinc alkyl/air systems as radical initiators for organic reactions

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Abstract

This paper reports a series of comparative experiments on the activity of carbon- and oxygen-centred radical species in a model reaction of the radical addition of THF to imines mediated by a series of zinc alkyl/air reaction systems. The study strongly contradicts the notion that generally R˙ radicals are the initiating species in organic reactions mediated by RnM/air systems, and simultaneously demonstrates that oxygen-centred radical species are the key intermediates responsible for the initiation process. In addition, a new efficient RZn(L)/air initiating system for radical organic reactions exampled by a model reaction of radical addition of THF to imines is developed. Moreover, the isolation and structural characterization of the first zinc alkylperoxide supported by a carboxylate ligand, [Zn43-OOtBu)34-O)(O2CEt)3]2, as well as the novel octanuclear zinc oxo(alkoxide) aggregate with entrapped O–THF species, [Zn44-O)(μ3-2-O–THF)(O2CEt)5]2, provide clear mechanistic signatures for the mode of function of the RZn(O2CR′)/air system.

Graphical abstract: Development of zinc alkyl/air systems as radical initiators for organic reactions

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Publication details

The article was received on 16 Feb 2015, accepted on 19 Mar 2015 and first published on 19 Mar 2015


Article type: Edge Article
DOI: 10.1039/C5SC00600G
Citation: Chem. Sci., 2015,6, 3102-3108
  • Open access: Creative Commons BY-NC license
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    Development of zinc alkyl/air systems as radical initiators for organic reactions

    M. Kubisiak, K. Zelga, W. Bury, I. Justyniak, K. Budny-Godlewski, Z. Ochal and J. Lewiński, Chem. Sci., 2015, 6, 3102
    DOI: 10.1039/C5SC00600G

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