Catalyst-controlled stereodivergent synthesis of polysubstituted alkenes.

The strategic utilization of earth-abundant transition metals in catalysis has emerged as a trans-formative movement in advancing of synthetic chemistry. Despite notable progress, the potential of leveraging diverse geometric configurations of these catalysts to achieve divergent synthesis remains largely untapped. In this work, we present a stereodivergent three-component borylfunctionalization of alkynes, enabled by ligand-modulated geometric variations in nickel catalysts. This approach provides a versa-tile platform for the stereodivergent synthesis of two classes of valuable polysubstituted alkene building blocks, a challenging feat in organic synthesis. Its practical utility is showcased by the rapid construction of biologically relevant molecules. Mechanistic studies support that different geometric configurations of nickel catalysts display distinct reactivity during key reaction steps, leading to the observed stereochemical outcomes.