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 reductant, 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 S_N2 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.