Nickel-catalyzed switchable 1,3-dienylation and enantioselective allenylation of phosphine oxides.

ABSTRACT

The development of general catalytic methods for the regio- and stereoselective construction of phosphoryl derivatives from identical substrates remains a formidable challenge in organic synthesis. Enabled by the newly developed BDPP-type ligands, we disclosed a nickel-catalyzed allenylation of phosphine oxides rationally and predictably, allowing the construction of versatile chiral allenylphosphoryl derivatives with high enantiopurity (up to 94% e.e.). Alternatively, using an achiral phosphine ligand dcypbz under acidic conditions, we achieved a regiochemical switch of the 1,3-dienylation to afford functionalized phosphinoyl 1,3-butadienes (up to 93% yield). The salient features of this method include switchable reactivity, broad substrate scope, readily available feedstock, single-step preparation, and high asymmetric induction.