Highly active, chemo- and enantioselective Pt-SPO catalytic systems for the synthesis of aromatic carboxamidesElectronic supplementary information (ESI) available. CCDC 1061952–1061957, 1062002. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5cy00627a

Platinum complexes modified with a chiral non-racemizing SPO preligand 1have been applied in the hydration of aromatic nitriles. [Pt(1)3Cl]Cl formed readily from Pt(COD)Cl2. The chiral secondary phosphine oxide complex showed moderate activity in the hydration of para- and meta-substituted benzonitriles, but failed in converting the ortho-substituted derivatives. The hydride complex PtH(PR2OH)(PR2O–HOR2P) (PR2OH = 1) formed from Pt(PPh3)4and 1, and the cationic complex derived from [Pt(1)3Cl]Cl viadirect chloride abstraction with AgNO3were proven to be considerably more active, allowing us to extend the scope to the hydration of ortho-substituted aromatic nitriles, including axially chiral [1,1′-binaphthalene]-2,2′-dicarbonitrile. In the hydration of the racemic dinitrile, successful kinetic resolution has been achieved. The catalysts derived from non-racemizing 1are the first chiral transition metal–SPO complexes that provide kinetic resolution in the hydration of a racemic chiral nitrile.