Highly Stereoselective and Efficient Hydrosilylation of Terminal Alkynes Catalyzed by [RuCl2(p-cymene)]2

Na, Youngim; Chang, Sukbok

doi:10.1021/ol0059697

Cited by 157 publications

(69 citation statements)

References 14 publications

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“…This finding is noteworthy as a means of accessing α-vinylmetal species in general. Access to α-vinylsilanes 12,19,20 or to other α-metalloid species (boron, tin, etc.) in a general and efficient manner is quite limited.…”

Section: Reaction Discovery Optimization and Markovnikov Hydrosilylamentioning

confidence: 99%

Alkyne Hydrosilylation Catalyzed by a Cationic Ruthenium Complex: Efficient and General Trans Addition

2005

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The complex [Cp*Ru(MeCN) 3 ]PF 6 is shown to catalyze the hydrosilylation of a wide range of alkynes. Terminal alkynes afford access to α-vinylsilane products with good regioselectivity. Deuterium labeling studies indicate a clean trans addition process is at work. The same complex is active in internal alkyne hydrosilylation, where absolute selectivity for the trans addition process is maintained. Several internal alkyne substrate classes, including propargylic alcohols and α,β-alkynyl carbonyl compounds, allow regioselective vinylsilane formation. The tolerance of a wide range of silanes is noteworthy, including alkyl-, aryl-, alkoxy-, and halosilanes. This advantage is demonstrated in the direct synthesis of triene substrates for silicon-tethered intramolecular DielsAlder cycloadditions.Metal-catalyzed simple addition reactions of alkynes are important synthetic processes and are desirable from the standpoint of synthetic efficiency and atom economy. Questions of regioand stereoselectivity become important considerations, and pathways affording syn addition are plentiful and well studied. Metal catalysis of trans addition processes-where new bonds must be formed on opposite sides of the alkyne-have only rarely been observed. Indeed, the possibility of creating direct trans addition processes which do not involve initial cis addition followed by E/Z isomerization is an exciting target. This paper describes our work studying trans addition processes in alkyne hydrosilylation with ruthenium catalysts to afford vinylsilane products.Vinyl-metal species are extremely important building blocks in organic synthesis. 1,2 Among these, vinylsilanes play a growing role due to their low cost, low toxicity, ease of handling, and simplicity of byproduct removal. Particularly significant is the potential of vinylsilanes as nucleophilic partners in palladium-catalyzed cross-coupling reactions. 3 Vinylsilanes are also useful as acceptors in conjugate addition reactions, as masked ketones through Tamao-Fleming oxidation, 4 and as terminators for cation cyclizations. 5 Unlike most other organometallic reagents-including in many cases organoboranes and organostannanes-vinylsilanes can be readily carried through many synthetic operations.However, the utility of vinylsilanes has been inhibited by the inconvenience of accessing stereo-and regio-defined vinylmetal compounds. Among the possible routes to these compounds, hydrosilylation of alkynes represents the most straightforward, atom-economical access. 6 Classical platinum catalysis 7 provides clean cis addition to (E)-vinylsilanes (2), and ligand tuning has made this a very regioselective process as well. 8 In addition, there has been significant progress using a variety of metal-catalyzed approaches to provide stereodefined, 1,2-substituted vinylsilanes of the form 1 or 2. There has been no reported general access to bmtrost@stanford.edu. NIH Public Access NIH-PA Author ManuscriptNIH-PA Author Manuscript NIH-PA Author Manuscript 1,1-disubstituted vinylsilanes 9 (3) a...

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Section: Reaction Discovery Optimization and Markovnikov Hydrosilylamentioning

confidence: 99%

Alkyne Hydrosilylation Catalyzed by a Cationic Ruthenium Complex: Efficient and General Trans Addition

2005

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“…[14] It involves the decarbonylation of ReBr(CO) 5 to form 16-electron intermediate ReBr-(CO) 4 , [15] which displays the catalytic activity of a transition metal Lewis acid catalyst. [16] Also, it cannot be ruled out that the present hydrosilylation reaction proceeds through the similar mechanism [17] as the late transition metal complex catalyzed hydrosilylation reaction that includes an oxidative addition step of the Si-H bond to the rhenium complex to generate a Re(H)Si species.…”

Section: Full Papermentioning

confidence: 99%

“…[1] A number of examples of the catalytic addition of hydrosilanes to alkynes catalyzed by a variety of transition metal complexes such as platinum, [2] rhodium, [2b,2d,3] ruthenium, [4] and other metal complexes [5] have been welldocumented in the literature. Conversely, the investigation of the addition reactions of alkenes with hydrosilanes have focused on the use of electron-deficient hydrosilanes such as HSiR n X 3-n (X = Cl, n = 0, 1) and H m SiR 4-m (m = 2, 3) in the presence of the late-transition-metal complexes.…”

Section: Introductionmentioning

confidence: 99%

Highly Regioselective Rhenium‐Catalyzed Hydrosilylation of Styrenes

Zhao

Hua

2006

Eur J Org Chem

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“…[3,4] Other noteworthy reports on the preparation of  -vinylsilanes include the hydrosilylation of terminal alkynes directed by hydroxy groups [5] or the silylcupration of terminal alkynes. [6] Although inner-sphere mechanisms seem to explain most of the selectivities hitherto reported, we recently proposed the first ionic outer-sphere mechanism for the hydrosilylation of terminal alkynes, substantiated by DFT calculations.…”

mentioning

confidence: 99%

Preferential α‐Hydrosilylation of Terminal Alkynes by Bis‐N‐Heterocyclic Carbene Rhodium(III) Catalysts

et al. 2015

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Abstract. We describe a bis-N-heterocyclic carbene Rhodium(III) complex, featuring two trifluoroacetato ligands, that affords a variety of α-vinylsilanes in good yields by hydrosilylation of terminal alkynes. Selectivities around 7:1 α/β-(E) were reached, while the β-(Z) product was only marginally obtained. This example sharply contrasts with the β-(Z)-selectivity observed for its parent diiodido complex Vinylsilanes are valuable building blocks in organic synthesis and, therefore, new preparation methods that would pave the way to a more sustainable production of these compounds are of great interest.[1] Metal-catalyzed hydrosilylation of terminal alkynes is an efficient and atom economical route to vinylsilanes;[2] however, selectivity is a major issue for this reaction as three possible isomers may be obtained. The anti-Markovnikov syn-addition affords the  -(E)-vinylsilane, usually the major reaction product, while the anti-Markovnikov anti-addition gives the less frequent β-(Z)-vinylsilane.[3] On the other hand, Markovnikov additions to obtain selectively α-vinylsilanes are unusual. [3,4] Other noteworthy reports on the preparation of  -vinylsilanes include the hydrosilylation of terminal alkynes directed by hydroxy groups [5] or the silylcupration of terminal alkynes. [6] Although inner-sphere mechanisms seem to explain most of the selectivities hitherto reported, we recently proposed the first ionic outer-sphere mechanism for the hydrosilylation of terminal alkynes, substantiated by DFT calculations. The solvent, namely an acetone molecule, assists the heterolytic splitting of the Si-H bond by catalysts 1a and 1b (Figure 1). [7] Subsequently, the R3Si+ moiety is transferred by means of an oxocarbenium ion ([R3Si-O(CH3)2]+) to the substrate. Finally, nucleophilic attack of the hydrido ligand over the silylation product ([R3Si-C=C-R]+) affords selectively the β-(Z)-vinylsilane as a result of the steric interactions that govern the approach of R3Si-C=C-R+ to the hydrido ligand.

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Highly Stereoselective and Efficient Hydrosilylation of Terminal Alkynes Catalyzed by [RuCl₂(p-cymene)]₂

Cited by 157 publications

References 14 publications

Alkyne Hydrosilylation Catalyzed by a Cationic Ruthenium Complex: Efficient and General Trans Addition

Alkyne Hydrosilylation Catalyzed by a Cationic Ruthenium Complex: Efficient and General Trans Addition

Highly Regioselective Rhenium‐Catalyzed Hydrosilylation of Styrenes

Preferential α‐Hydrosilylation of Terminal Alkynes by Bis‐N‐Heterocyclic Carbene Rhodium(III) Catalysts

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