Atom‐Economical Synthesis of <i>Gem</i> ‐Borylsilylalkanes by Copper‐Catalyzed SiH Bond Insertion of <i>α</i> ‐Furyl Boryl Carbenes

The copper‐catalyzed SiH bond insertion of α ‐furyl boryl carbenes generated from BMIDA‐terminated enynones allows facile and atom‐economical synthesis of various gem ‐borylsilylalkanes. This reaction proceeds in moderate‐to‐good yields (up to 86%) under mild reaction conditions. The potential synthetic applicability of this new protocol is illustrated by gram‐scale experiment, three‐component cascade synthesis, and synthetic transformation of the products. Moreover, this methodology can be successfully extended to GeH and SnH bond insertions, leading to gem ‐borylgermylalkanes and gem ‐boryltinylalkanes in good yields.