73654-55-4

Upstream product

• 4187-87-5 1-Phenyl-2-propyn-1-ol 
• 849518-46-3 1-phenyl-3-(triethylsilyl)prop-2-yn-1-ol 
• 4173-48-2 (1-((2-methoxypropan-2-yl)oxy)prop-2-yn-1-yl)benzene 
• 617-86-7 triethylsilane 

Downstream Products

• 51795-73-4 1-phenyl-2-pentene 
• 16002-93-0 (E)-1-phenyl-1-pentene 
• 37549-95-4 (Z)-pent-2-en-1-ylbenzene 
• 1612873-47-8 benzyl (E)-3-(triethylsilyl)-1-phenylallylcarbamate 
• 13506-93-9 1-(Triethylsilyl)-3-phenylpropan-3-one 

Relevant academic research and scientific papers

INVESTIGATION OF THE FACTORS CONTROLLING THE REGIOSELECTIVITY OF THE HYDROSILYLATION OF ALKYNES CATALYSED BY trans-DI-μ-HYDRIDOBIS(TRICYCLOHEXYLPHOSPHINE)BIS(SILYL)DIPLATINUM COMPLEXES

The hydrosilylation of terminal and internal alkynes and also of some hydroxy-alkynes catalysed by trans-di-μ-hydridobis(tricyclohexylphosphine)bis(silyl)diplatinum complexes is described.These diplatinum complexes are very efficient catalysts for such hy

Markovnikov Hydrosilylation of Alkynes with Tertiary Silanes Catalyzed by Dinuclear Cobalt Carbonyl Complexes with NHC Ligation

Metal-catalyzed hydrosilylation of alkynes is an ideal atom-economic method to prepare vinylsilanes that are useful reagents in the organic synthesis and silicone industry. Although great success has been made in the preparation of β-vinylsilanes by metal-catalyzed hydrosilylation reactions of alkynes, reported metal-catalyzed reactions for the synthesis of α-vinylsilanes suffer from narrow substrate scope and/or poor selectivity. Herein, we present selective Markovnikov hydrosilylation reactions of terminal alkynes with tertiary silanes using a dicobalt carbonyl N-heterocyclic carbene (NHC) complex [(IPr)2Co2(CO)6] (IPr = 1,3-di(2,6-diisopropylphenyl)imidazol-2-ylidene) as catalyst. This cobalt catalyst effects the hydrosilylation of both alkyl- and aryl-substituted terminal alkynes with a variety of tertiary silanes with good functional group compatibility, furnishing α-vinylsilanes with high yields and high α/β selectivity. Mechanistic study revealed that the stoichiometric reactions of [(IPr)2Co2(CO)6] with PhCCH and HSiEt3 can furnish the dinuclear cobalt alkyne and mononuclear cobalt silyl complexes [(IPr)(CO)2Co(μ-ν2:ν2-HCCPh)Co(CO)3], [(IPr)(CO)2Co(μ- ν2:ν2-HCCPh)Co(CO)2(IPr)], and [(IPr)Co(CO)3(SiEt3)], respectively. Both dicobalt bridging alkyne complexes can react with HSiEt3 to yield α-triethylsilyl styrene and effect the catalytic Markovnikov hydrosilylation reaction. However, the mono(NHC) dicobalt complex [(IPr)(CO)2Co(μ- ν2:ν2-HCCPh)Co(CO)3] exhibits higher catalytic activity over the di(NHC)-dicobalt complexes. The cobalt silyl complex [(IPr)Co(CO)3(SiEt3)] is ineffective in catalyzing the hydrosilylation reaction. Deuterium labeling experiments with PhCCD and DSiEt3 indicates the syn-addition nature of the hydrosilylation reaction. The absence of deuterium scrambling in the hydrosilylation products formed from the catalytic reaction of PhCCH with a mixture of DSiEt3 and HSi(OEt)3 hints that mononuclear cobalt species are less likely the in-cycle species. These observations, in addition to the evident of nonsymmetric Co2C2-butterfly core in the structure of [(IPr)(CO)2Co(μ- ν2:ν2-HCCPh)Co(CO)3], point out that mono(IPr)-dicobalt species are the genuine catalysts for the cobalt-catalyzed hydrosilylation reaction and that the high α selectivity of the catalytic system originates from the joint play of the dicobalt carbonyl species to coordinate alkynes in the Co(μ- ν2:ν2-HCCR′)Co mode and the steric demanding nature of IPr ligand.

Palladium-catalyzed reaction of γ-silylated allyl acetates proceeding through 1,2-shift of a substituent on silicon

The palladium-catalyzed reaction of γ-silylated allyl acetates with water in the presence of CsF induces a previously unprecedented 1,2-shift of a substituent on silicon to produce allylsilanes in situ. The catalytic activity of the palladium increased when using an electron-poor phosphine ligand possessing fluorinated substituents. Further investigation of the reaction revealed that the approximate order of the migratory aptitude of groups from silicon was PhC≡C, allyl > Bn > Ph, vinyl > alkyl (Me, Et). A density functional theory study was employed to explore the reaction mechanism. Finally, the Hosomi–Sakurai-type allylation of aldehydes with in situ-generated α,γ-disubstituted allylsilanes was also investigated.

Silicon-directed rhenium-catalyzed allylic carbaminations and oxidative fragmentations of γ-silyl allylic alcohols

A highly regioselective allylic substitution of β-silyl allylic alcohols has been achieved that provides the branched isomer as a single product. This high level of regiocontrol is achieved through the use of a vinyl silane group that can perform a Hiyama coupling providing 1,3-disubstituted allylic amines. An unusual oxidative fragmentation product was also observed at elevated temperature that appears to proceed by a Fleming-Tamao-type oxidation-elimination pathway.

Fluorinated N-heterocyclic carbenes rhodium (I) complexes and their activity in hydrosilylation of propargylic alcohols

The synthesis of three rhodium complexes with fluorinated N-heterocyclic carbenes of general formula [RhCOD(NHC)Cl] where COD = 1,5-cyclooctadiene, NHC = N-heterocyclic carbene [1-butyl-3-pentafluorobenzyl-imidazol-2-ylidene (1), 1-benzyl, 3-pentafluorobe

A Selective Synthesis of (E)-Vinylsilanes by Cationic Rhodium Complex-Catalyzed Hydrosilylation of 1-Alkynes and Tandem Hydrosilylation/Isomerization Reaction of Propargylic Alcohols to β-Silyl Ketones

(E)-Vinylsilanes were obtained with high selectivities by BF4/2PPh3-catalyzed hydrosilylation of 1-alkynes with triethylsilane.A wide range of 1-alkynes were used.The hydrosilylation of propargylic alcohols with triethylsilane gave (E)-γ-silyl a

Carbon-13 nuclear magnetic resonance spectra of E-silyl-alkenes

Carbon-13 nmr chemical shifts of a number of E-silyl-alkenes containing the silyl substituent at an sp2 carbon atom are presented.Assignments of the chemical shifts have been made by noting systematic variations in the spectra with changes in s