Solvent-Regulated Enantiodivergent Construction of Secondary Phosphine Oxides with P-Stereogenicity.

Solvents play a pivotal role in organic synthesis, affecting the reaction kinetics and selectivity. Solvent polarity efficiently tunes enantioselectivity in asymmetric catalysis to enable the enantiodivergent construction of chiral compounds. Chiral phosphorus architectures are essential scaffolds in catalysis, pharmaceuticals, and agrochemistry. We report a solvent-regulated nickel-catalyzed dienyl substitution of primary phosphine oxides, affording P-stereogenic R and S enantiomers. This low-cost, simple protocol allows the stereodivergent synthesis of chiral secondary phosphine oxides as key synthons for diverse P-stereogenic compounds.