Nickel‐Catalyzed Boron‐Mediated Saturative Trifunctionalization of Alkynes

Converting simple alkynes into fully substituted alkanes-installing three distinct groups via a sequential one‑pot process-remains a formidable challenge. Herein, we report a boron-mediated, nickel-catalyzed strategy that achieves this transformation, enabling the modular assembly of valuable 1,1-diarylalkanes from both simple alkynyl tetracoordinate borons and N-acylglutarimides. The reaction proceeds with high regio- and chemoselectivity under mild conditions, exhibiting good functional group tolerance across both coupling partners. Mechanistic studies support a unique reaction pathway involving dual 1,2-metallate shifts, with water serving as the terminal proton source. The synthetic utility is demonstrated through one-pot synthesis, late-stage functionalization of drugs, gram-scale reactions, and versatile downstream transformations of the products. This strategy represents a distinct strategy that differs from stepwise alkyne reduction, offering a useful disconnection for complex alkane synthesis starting from alkynyl tetracoordinate borons or terminal alkynes via one‑pot borylation.