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Issue 21, 2011
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Copper(II) complexes incorporating poly/perfluorinated alkoxyaluminate-type weakly coordinating anions: Syntheses, characterization and catalytic application in stereoselective olefin aziridination

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Abstract

The synthesis and characterization of a series of cationic copper(II) complexes of the type [Cu(NCR)6][Al(OC(CF3)2R′)4]2 (R = CH3, Ph; R′ = CF3, Ph, PhCH3), incorporating poly/perfluoronated alkoxyaluminates as weakly coordinating anions (WCAs) is presented. Aziridination of various olefins, such as the unreactive olefinse.g.ethylhex-2-enoate and 1-decene, with N-tosyliminophenyliodinane catalyzed by [Cu(NCR)6][Al(OC(CF3)2R′)4]2 affords very good yields (up to 96%) and high TOFs (up to 5000 h−1) under mild conditions. Using disubstituted olefins as substrates, high stereoselectivities are obtained at room temperature. The to date highest cis : trans ratio (98 : 2) of the obtained aziridines is achieved for cis-stilbene in good yield (85%) as well as promising TOF (> 2000 h−1). The investigation of the solvent effect on yield and selectivity reveals that for certain oleophilic substrates (1-decene), less polar solvents, such as dichloromethane are a better choice than acetonitrile, which is commonly considered as the best solvent for olefin aziridination. Accordingly, a mechanism involving a paramagnetic copper nitrene intermediate with both concerted and stepwise pathways is proposed.

Graphical abstract: Copper(ii) complexes incorporating poly/perfluorinated alkoxyaluminate-type weakly coordinating anions: Syntheses, characterization and catalytic application in stereoselective olefin aziridination

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Publication details

The article was received on 19 Feb 2011, accepted on 21 Mar 2011 and first published on 26 Apr 2011


Article type: Paper
DOI: 10.1039/C1DT10280J
Citation: Dalton Trans., 2011,40, 5746-5754
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    Copper(II) complexes incorporating poly/perfluorinated alkoxyaluminate-type weakly coordinating anions: Syntheses, characterization and catalytic application in stereoselective olefin aziridination

    Y. Li, J. He, V. Khankhoje, E. Herdtweck, K. Köhler, O. Storcheva, M. Cokoja and F. E. Kühn, Dalton Trans., 2011, 40, 5746
    DOI: 10.1039/C1DT10280J

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