Hydrosilylation of alkynes catalyzed by ruthenium carbene complexes

Catalytic transformation of phenylacetylene mediated by phosphine-free ruthenium alkylidene complexes

“…On the other hand, second-generation ruthenium alkylidene catalysts have also been reported as initiators mediating the hydrosilylation of alkynes [26], the polymerization of ortosubstituted phenylacetylenes [27], hydroxyacetylenes [28], and 1,6-heptadiynes [29]. Although second-generation phosphine-free ruthenium catalysts have been reported as inactive in the dimerization of silylacetylenes [19], to the best of our knowledge those complexes have not been used as catalysts for the intermolecular cyclotrimerization of 1-alkynes.…”

Synthesis of 3‐Deoxy Glycals via Tandem Metathesis Sequences and Their Use in an Intermolecular Heck Arylation

“…[67,68] We thought that our metathesis precursor 10 would be well suited to access dihydropyrans or glycals with two orthogonal protecting groups at C4 and C6 position, for instance one benzyl ether and one silyl ether. While conventional silylation of 10 with a silyl halide or triflate would be an obvious solution, we pursued an alternative route that relies on the ability of ruthenium carbenes to activate Si-H bonds: for instance, Grubbs' catalysts are known to catalyze the hydrosilylation of alkynes [69][70][71] or the hydrogenation of alkenes with silanes. [72] In addition, we had previously reported that triethylsilane is also a suitable additive to promote the double bond migration step of the tandem RCM/isomerization sequence.…”

Xphos ligand and platinum catalysts: A versatile catalyst for the synthesis of functionalized β-(E)-vinylsilanes from terminal alkynes

“…Use of other non-protic polar solvents such as DMF or NMP provided a slightly lower b-(E)-selectivity (entries 4 and 5). Employment of both EtOH, HFIP or H 2 O can replace THF to achieve same level of selectivity (entries [6][7][8].…”

“…With (EtO) 2 MeSiH, the branched a-isomer is best obtained in the presence of a cationic Ru complex [Cp * Ru(MeCN) 3 ]PF 6 [6]. Using ruthenium carbene complexes [7] or [RuCl 2 (p-cymene)] 2 [8] as well as [Cp * IrCl 2 ] 2 [9] catalysts, selective formation of stereoisomeric b-(Z)-vinylsilanes, is generally achieved. The formation of the third b-(E)-isomer is best accomplished by using Rh-[10] Ir- [11] and Pd-based [12] catalysts.…”