Cobalt‐Catalyzed Dehydrogenative C−H Silylation of Alkynylsilanes

Abstract

Herein, we report that a cobalt catalyst permits the general synthesis of substituted alkynylsilanes through dehydrogenative coupling of alkynylsilanes and hydrosilanes. Several silylated alkynes, including di-and trisubstituted ones, were prepared in a one-step procedure. Thirty-seven compounds were synthesized for the first time by applying our [a] H.

Photochemical alkynylation of hydrosilanes by iron catalysis

“…Since the first strategy reported by Voronkov, 6 a number of metal-catalyzed approaches involving cross dehydrogenative coupling between alkynes and hydrosilanes have been developed. 7–9 A homogeneous catalytic system containing Pt, Cu, Al, Yb, Sm, Ir, Ca, Zn and Co, as well as heterogeneous catalysis such as by MgO, KNH 2 /Al 2 O 3 , Au/OMS-2 (OCM: octahedral molecular sieves), Au 0.4 Pd 0.6 @PEG2000 and AuNPore (Ag) are becoming the mainstream gradually. However, these established metal-catalyzed routes retain some drawbacks regarding to (1) high temperature reaction conditions, (2) highly basic conditions, (3) expensive or rare-earth metals, (4) complicated pre-activation of the catalysts, and (5) poor substrate generality in the case of hydrosilanes.…”

Transition Metal‐Free Catalytic C−H Silylation of Terminal Alkynes with bis(Trimethylsilyl)acetylene Initiated by KHMDS

“…Moreover, with a few exceptions, [14][15][16][17] the vast majority of such strategies are based on catalysis utilizing transition metals. [18][19][20][21] This in turn can lead to reduced selectivity and efficiency due to possible competition between coupling and addition routes (hydrosilylation). In contrast, the concept of using silylacetylenes as an atypical coupling partner has occasionally been deployed and these strategies are not without their own disadvantage, including the use of fluoride reagents or/and expensive crown ethers, harsh conditions, lower chemoselectivity (e. g., the dimerization of phenylacetylenes) and narrow substrate scope.…”

“…Unfortunately, this approach is completely impractical for the preparation of a highly important TMS‐protecting group (TMS=trimethylsilyl), due to the pyrophoricity of gaseous Me 3 SiH and its lightest congeners. Moreover, with a few exceptions, [14–17] the vast majority of such strategies are based on catalysis utilizing transition metals [18–21] . This in turn can lead to reduced selectivity and efficiency due to possible competition between coupling and addition routes (hydrosilylation).…”

Silicon–nitrogen bond formation via dealkynative coupling of amines with bis(trimethylsilyl)acetylene mediated by KHMDS

“…Sustainable and eco-friendly synthetic approaches proceeded by the main-group catalysis have gained recent significant attention. [39][40][41][42][43][44] On the basis of our recent success in activating silylacetylenes under sustainable catalysis, [45][46][47][48] we reasoned that an appropriate catalytic manifold could provide an efficient platform to generate diversified libraries of trimethylsilylated amines. In this communication, we report on the catalytic silylation of primary amines with bis(trimethylsilyl)acetylene (BTMSA) for the construction of N-Si bonds via dealkynative coupling, by using potassium bis(trimethylsilylamide) as the catalyst (Figure 1, f).…”