Issue 66, 2018

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

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

Supplementary files

Article information

Article type
Communication
Submitted
28 Jun 2018
Accepted
24 Jul 2018
First published
24 Jul 2018

Chem. Commun., 2018,54, 9139-9142

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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