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Issue 66, 2018
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The open d-shell enforces the active space in 3d metal catalysis: highly enantioselective chromium(II) pincer catalysed hydrosilylation of ketones

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Abstract

Bis(oxazolinyldimethylmethyl)pyrrol (PdmBox) stereodirecting ligands provided the key to the chromium(II)-catalysed highly enantioselective hydrosilylation of ketones. A rare square planar, chiral chromium(II) alkyl complex was found to serve as a potent precatalyst for the reduction of a broad range of aryl alkyl and dialkyl ketone derivatives. The stereoelectronic preference of the open d4 shell of chromium(II) firmly locks the molecular catalyst in a square planar geometry giving rise to two blocked quadrants of the coordination sphere. This earth-abundant base metal catalytic platform produces the corresponding chiral alcohols in excellent isolated yields with up to 98 %ee under mild reaction conditions (−40 °C to rt) and at low catalyst loadings (as low as 0.5 mol%).

Graphical abstract: The open d-shell enforces the active space in 3d metal catalysis: highly enantioselective chromium(ii) pincer catalysed hydrosilylation of ketones

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Publication details

The article was received on 28 Jun 2018, accepted on 24 Jul 2018 and first published on 24 Jul 2018


Article type: Communication
DOI: 10.1039/C8CC05172K
Citation: Chem. Commun., 2018,54, 9139-9142
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    The open d-shell enforces the active space in 3d metal catalysis: highly enantioselective chromium(II) pincer catalysed hydrosilylation of ketones

    C. H. Schiwek, V. Vasilenko, H. Wadepohl and L. H. Gade, Chem. Commun., 2018, 54, 9139
    DOI: 10.1039/C8CC05172K

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