Catalytic Silylation of Alkynyl C(sp)–H Bonds with <i>tert</i> ‐Butyl‐Substituted Silyldiazenes

Abstract The deprotonative silylation of terminal alkynes constitutes one of the most privileged strategies to prepare alkynylsilanes owing to the relatively high acidity of C(sp)–H bonds. While the key deprotonation step is usually mediated by stoichiometric amounts of strong Brønsted bases (e.g., n BuLi) followed by the trapping of the corresponding acetylide with electrophilic silylating reagents, such a sequence can also be transposed to a catalytic regime through pro‐base strategies. We herein demonstrate that N ‐ tert ‐butyl‐ N ’‐silyldiazenes ( t Bu–N = N– Si ) widen the repertoire of silylated pro‐bases that can be used to promote the silylation of a range of terminal alkynes. These reactions are initiated with only catalytic amounts of inexpensive potassium hydroxide, proceed rapidly at room temperature, exhibit broad scope, and allow seamless one‐pot integration with downstream transformations of alkynylsilane products.