97779-83-4

Upstream product

• 917-92-0 3,3-Dimethylbut-1-yne 
• 3839-31-4 dimethyl(phenyl)silyllithium 
• 74-88-4 methyl iodide 
• 78-79-5 isoprene 
• 766-77-8 Dimethylphenylsilane 
• 17156-64-8 (dimethylphenylsilyl)acetylene 
• 677-22-5 tert-butylmagnesium chloride 
• 108-86-1 bromobenzene 
• 1252913-97-5 1-(dimethylphenylsilyl)-3,3-dimethyl-2-butanol 
• 558-17-8 tert-Butyl iodide 
• 768-33-2 phenyldimethylsilyl chloride 
• 630-19-3 pivalaldehyde 
• 1833-51-8 chloromethyldimethylphenylsilane 
• 64-17-5 ethanol 

Downstream Products

• 29569-93-5 (E)-4,4-dimethyl-1-phenylpent-2-en-1-one 

Relevant academic research and scientific papers

Synthesis and characterization of a free phenylene bis(N-heterocyclic carbene) and its di-Rh complex: Catalytic activity of the di-Rh and CCC-NHC Rh pincer complexes in intermolecular hydrosilylation of alkynes

1,3-Bis(3-butylimidazolium-1-yl)benzene diiodide (1) was reacted with Li(2,2,6,6-tetramethylpiperidine) yielding the free bis-carbene, 1,3-bis(3-butylimidazol-2-ylidene-1-yl)benzene (3), which has been spectroscopically characterized. Combining the free b

Rh(I)/(III)-N-Heterocyclic Carbene Complexes: Effect of Steric Confinement Upon Immobilization on Regio- and Stereoselectivity in the Hydrosilylation of Alkynes

Rh(I) NHC and Rh(III) Cp* NHC complexes (Cp=pentamethylcyclopentadienyl, NHC=N-heterocyclic carbene=pyrid-2-ylimidazol-2-ylidene (Py?Im), thiophen-2-ylimidazol-2-ylidene) are presented. Selected catalysts were selectively immobilized inside the mesopores

Direct Access to α,β-Unsaturated Ketones via Rh/MgCl2-Mediated Acylation of Vinylsilanes

We report herein the facile and practical construction of α,β-unsaturated ketones via rhodium-catalyzed direct acylation of vinylsilanes with readily available and abundant carboxylic acids. This protocol features access to a diverse array of synthetically useful functionalities with moderate to excellent yields. More importantly, the late-stage functionalization of pharmaceuticals was also realized with synthetically useful yield.

β-(Z) Selectivity Control by Cyclometalated Rhodium(III)-Triazolylidene Homogeneous and Heterogeneous Terminal Alkyne Hydrosilylation Catalysts

The cyclometalated Rh(III)-NHC compounds [Cp*RhI(C,C′)-Triaz] (Triaz = 1,4-diphenyl-3-methyl-1,2,3-triazol-5-ylidene) and [Cp*RhI(C,C′)-Im] (Im = 1-phenyl-3-methyl-imidazol-2-ylidene) are efficient catalysts for the hydrosilylation of terminal alkynes wit

Carboxylate-Assisted β-(Z) Stereoselective Hydrosilylation of Terminal Alkynes Catalyzed by a Zwitterionic Bis-NHC Rhodium(III) Complex

The zwitterionic compound [Cp*RhCl{(MeIm)2CHCOO}] is an efficient catalyst for the hydrosilylation of terminal alkynes with excellent regio- and stereoselectivity toward the less thermodynamically stable β-(Z)-vinylsilane isomer under mild reaction conditions. A broad range of linear 1-alkynes, cycloalkyl acetylenes, and aromatic alkynes undergo the hydrosilylation with HSiMe2Ph to afford the corresponding β-(Z)-vinylsilanes in quantitative yields in short reaction times. The reaction of aliphatic alkynes with HSiEt3 is slower, resulting in a slight decrease of selectivity toward the β-(Z)-vinylsilane product, which is still greater than 90%. However, a significant selectivity decrease is observed in the hydrosilylation of aromatic alkynes because of the β-(Z) → β-(E) vinylsilane isomerization. Moreover, the hydrosilylation of bulky alkynes, such as t-Bu-CCH or Et3SiCCH, is unselective. Experimental evidence suggests that the carboxylate function plays a key role in the reaction mechanism, which has been validated by means of density functional theory calculations, as well as by mass spectrometry and labeling studies. On the basis of previous results, we propose an ionic outer-sphere mechanism pathway in which the carboxylate fragment acts as a silyl carrier. Namely, the hydrosilylation mechanism entails the heterolytic activation of the hydrosilane assisted by the carboxylate function to give the hydrido intermediate [Cp*RhH{(MeIm)2CHCOO-SiR3}]+. The transference of the silylium moiety from the carboxylate to the alkyne results in the formation of a flat β-silyl carbocation intermediate that undergoes a hydride transfer from the Rh(III) center to generate the vinylsilane product. The outstanding β-(Z) selectivity results from the minimization of the steric interaction between the silyl moiety and the ligand system in the hydride transfer transition state.

Silver-catalyzed regioselective carbomagnesiation of alkynes with alkyl halides and Grignard reagents

A silver-catalyzed carbomagnesiation of alkynes with alkyl halides and Grignard reagents afforded alkenyl Grignard reagents regioselectively, where the alkyl group of the alkyl halide, but not that of the Grignard reagent, was introduced into the alkyne.

The β-silicon effect. 4: Substituent effects on the solvolysis of 1-alkyl-2-(aryldimethylsilyl)ethyl trifluoroacetates

Solvolysis rates of 2-(aryldimethylsilyl)-1-methylethyl and 2-(aryldimethylsilyl)-1-tert-butylethyl trifluoroacetates were determined conductimetrically in 60% (v/v) aqueous ethanol. The effects of aryl substituents at the silicon atom on the solvolysis rates at 50 °C were correlated with σmacr; parameters of r+ = 0.15 with the Yukawa-Tsuno equation, giving ρ values of-1.5 for both secondary α-Me and α-tert-Bu systems. The ρ values for those secondary systems are less negative than-1.75 for the 2-(aryldimethylsilyl)ethyl system that proceeds by the Eaborn (non-vertical) mechanism, while they are distinctly more negative than-0.99 for 2-(aryldimethylsilyl)-1-phenylethyl system that should proceed by the Lambert (vertical) mechanism. There was a fairly linear relationship between the reaction constants (ρ) for the β-silyl substituent effects and the solvolysis reactivities for a series of β-silyl substrates. The solvolyses of the α-Me and tert-Bu substrates proceed through the transition state (TS) with an appreciable degree of the β-silyl participation, close to the Eaborn (non-vertical) TS rather than to the Lambert (vertical) TS. Copyright

Silver-catalyzed carbomagnesiation of terminal aryl and silyl alkynes and enynes in the presence of 1,2-dibromoethane

Regioselective carbomagnesiation of terminal alkynes and enynes with alkyl Grignard reagents has been achieved by the combined use of a silver catalyst and 1,2-dibromoethane. The Royal Society of Chemistry 2009.

Selective hydrosilylation of 1-alkynes using iridium catalyst with biphosphinine ligand

The iridium-catalyzed hydrosilylation of alkynes in the presence of 4,4′,5,5′-tetramethylbiphosphinine (tmbp) has been explored. The hydrosilylation of alkynes in the presence of tmbp proceeds effectively to give β-(E)-vinylsilanes highly selectively in m

Synthesis and application of a new selenoplatinum catalyst

The reaction of 4-methyl-5-ethoxycarbonyl-1,2,3-selenadiazole with (PPh3)4Pt leads to the formation of a new platinum-containing heterocyclic system. It was found that the selenoplatinum complex is a selective catalyst for the hydrosilylation of terminal alkynes to yield β-(Z)- and β-(E)-silylethylenes.