Ni-H-Catalyzed Regioselective Hydroalkylation of Terminal Alkynes with α-Bromo Phosphonates

We present here a versatile and efficient Ni-H-catalyzed hydroalkylation reaction of terminal alkynes and α-bromo phosphonates with Markovnikov selectivity, yielding a range of allylic phosphate terminal alkenes. This reaction demonstrates a broad substrate scope and excellent functional group compatibility, including those with complex structural motifs found in natural products and pharmaceuticals. The practical applicability is demonstrated through gram-scale reactions and product transformations. In addition, the methodology is also applicable to the substrates of benzyl bromides and bromo amides.