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

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 d(4) 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 degrees C to rt) and at low catalyst loadings (as low as 0.5 mol%).