Dehydrocondensation of trialkylsilanes with acetylene and monosubstituted acetylenes

Dehydrogenative Silylation of Terminal Alkynes with Hydrosilanes under Zinc–Pyridine Catalysis

“…However, it is rather surprising that simple alkynes with no functional group have been the focus of earlier studies 10,11. Furthermore, hydrosilylation of the alkyne frequently occurs as a side‐reaction 10a,b,d,g,h,k. As a reliable and sustainable process, we disclose herein the zinc–pyridine‐catalyzed D.S.…”

Tuning the Selectivity of AuPd Nanoalloys towards Selective Dehydrogenative Alkyne Silylation

“…As was mentioned above, the direct dehydrogenative coupling of alkynes and hydrosilanes would be most appealing considering atom economy and indeed few reports along those lines have appeared. Pukhnarevich and co‐workers disclosed the first transition‐metal‐catalyzed coupling of alkynes and hydrosilanes by using H 2 PtCl 6 in the presence of iodine to give the corresponding alkynylsilanes . Since this work, other homogeneous transition‐metal catalysts,– as well as strong bases or reducing agents, such as alkoxides, Na/HMPT, MgO, NaOH, LiAlH 4 ,, KNH 2 /Al 2 O 3 and NaHBEt 3 have been shown to mediate this transformation.…”

“…Both systems operate under similar conditions at 80 °C in toluene, and O 2 was applied as the terminal oxidant. Despite these recent advances, there is room for improvement, because existing methods work at elevated temperatures (100–120 °C),–, require laborious preparation of the catalyst,, lead to hydrosilylation byproducts,– need high catalyst loadings, and most severely show low tolerance towards functional groups –,––. Therefore, new easily accessible and bench‐stable catalysts that work under mild conditions are demanded.…”

Chemoselective Aerobic Cross‐Dehydrogenative Coupling of Terminal Alkynes with Hydrosilanes by a Nanoporous Gold Catalyst

“…In addition, LiAlH 4 , metal alkoxides, and alkali metal hydroxides have been developed as basic catalysts . However, these methods also have many drawbacks, such as formation of undesired hydrosilylation products,, poor substrate generality in the case of alkyne and/or hydrosilanes,,, complicated pre‐activation of catalysts,, requirement of hydrogen acceptors and/or additives,,,, modest yields and selectivities,,, highly basic conditions,– and necessity of large amounts of hydrosilanes . Alternatively, only few heterogeneous catalytic systems, such as MgO, KNH 2 /Al 2 O 3 , and Au/OMS‐2 (OCM: octahedral molecular sieves), have been reported to date .…”