An unprecedented Rauhut-Currier-type 1,6-conjugate addition has been developed. With chiral cyclohexane-based phosphine-amide catalyst 3 h, the 1,6-conjugate reaction has been achieved to produce chiral diarylmethine compounds in excellent yields (91-99 %) and enantioselectivities (92-98 % ee).

The first highly enantioselective cyanosilylation of α,α‐dialkoxy ketones enabled by a dual‐reagent catalysis has been developed. With the combination of a chiral bifunctional phosphine‐thiourea and methyl acrylate, the key organophosphorus zwitterion intermediate was generated in situ as a novel Lewis base, which catalyzed the enantioselective cyanosilylation reaction in excellent yields (up to 99 %) with good‐to‐excellent enantioselectivities (up to 94 % ee).