Manganese-Mediated C(sp)–Si Cross-Electrophile Coupling of Alkynyl Halides with Chlorosilanes

We present a manganese-mediated cross-electrophile coupling (XEC) that directly constructs C(sp)–Si bonds between alkynyl halides and chlorosilanes. By leveraging manganese as a bifunctional reductant/catalyst, this method enables a mild and operationally simple approach. Mechanistic studies reveal the in situ generation of key intermediates alkynylmanganese in amide media, which undergo SN2 substitution with chlorosilanes to afford diverse alkynylsilanes in high yields (up to 99%) with suppressed diyne byproducts. To our knowledge, this is the first discovery of alkynylmanganese species, derived from readily available alkynyl halides, for C(sp)–Si cross-electrophilic coupling. This work expands the scope of XEC in organosilicon chemistry and provides a robust alternative for C(sp)–Si bond formation.