21654-93-3

Upstream product

• 592-41-6 1-hexene 
• 775-12-2 diphenylsilane 

Downstream Products

• 1062505-07-0 S(R)-N-[(1R)-1-(hexyldiphenylsilyl)butyl]-2-methylpropane-2-sulfinamide 
• 1384451-97-1 N-(1-((hexyl)(diphenyl)silyl)ethyl)acetamide 

Relevant academic research and scientific papers

Hydrosilylation of alkenes catalyzed by Fe powder

A novel iron-catalyzed hydrosilylation of alkenes process under solvent-free conditions has been reported. The influence of the amount of Fe catalyst, reaction temperature and various alkenes and silanes on the hydrosilylation were investigated. High yields of adduct were obtained in the hydrosilylation of octene with MeCl2H, Me2ClSiH and Ph2SiH2 by using 10 mol% iron powder as a signal catalyst.

Metal-free photocatalytic hydrosilylation of olefins in the presence of photoinitiators

A convenient metal-free photocatalytic hydrosilylation of a variety of linear and cyclic alkenes has been investigated. It was found that the free radical type photoinitiator Irgacure 2959 had a better effect on the hydrosilylation reaction; using 3 mol%

Cobalt bis(2-ethylhexanoate) and terpyridine derivatives as catalysts for the hydrosilylation of olefins

A simple method for the hydrosilylation of olefins by using air-stable cobalt catalysts is developed. The catalyst system is composed of simple, cheap, and readily available cobalt(II) salts and well-defined terpyridine derivatives as cocatalysts or ligands, and the hydrosilylation processes can be processed smoothly under mild conditions without either Grignard reagents or NaHBEt3 as activator.

Highly active cobalt complex catalysts used for alkene hydrosilylation

A series of nitrogen phosphine ligands were synthesized, and the hydrosilylation reaction of alkenes catalyzed using MCl2 in the presence of these ligands was investigated. FeCl2/1(N1, N1, N2, N2-Tetrakis[(diphenylphosphino)methyl]ethane-1,2-diamine) showed low catalytic activity. MnCl2/1, CrCl3/1 and NiCl2/1 showed some catalytic activity. The CoCl2/N,P-ligand catalyst system showed high activity as well as excellent selectivity (The selectivity of the β-adduct was ~100%.) in the hydrosilylation reaction. CoCl2/1 showed the highest catalytic activity (~ >99.9% conversion of 1-octene). Additionally, no α-adduct, dehydrogenative silylation product and octane were detected.

Efficient alkene hydrosilation with bis(8-quinolyl)phosphine (NPN) nickel catalysts. The dominant role of silyl-over hydrido-nickel catalytic intermediates

A cationic nickel complex of the bis(8-quinolyl)(3,5-di-tert-butylphenoxy)phosphine (NPN) ligand, [(NPN)NiCl]+, is a precursor to efficient catalysts for the hydrosilation of alkenes with a variety of hydrosilanes under mild conditions and low catalyst loadings. DFT studies reveal the presence of two coupled catalytic cycles based on [(NPN)NiH]+and [(NPN)NiSiR3]+active species, with the latter being more efficient for producing the product. The preferred silyl-based catalysis is not due to a more facile insertion of alkene into the Ni-Si (vs.Ni-H) bond, but by consistent and efficient conversions of the hydride to the silyl complex.

The catalytic activity of alkali metal alkoxides and titanium alkoxides in the hydrosilylation of unfunctionalized olefins

The catalytic activities of titanium alkoxides and alkali metal alkoxides for hydrosilylation of unfunctionalized olefins have been studied. Titanium(IV) alkoxides showed excellent catalytic activity, while alkali metal alkoxides have low catalytic activity for the hydrosilylation of olefins. However, by using titanocene dichloride as an additive, alkali metal alkoxides showed also excellent catalytic property for hydrosilylation. In comparison with titanium alkoxides, no α-adduct was obtained by using alkali metal alkoxides/Cp2TiCl2 as catalysts.

Titanium-catalyzed hydrosilylation of olefins: A comparison study on Cp2TiCl2/Sm and Cp2TiCl2/LiAlH4 catalyst system

Hydrosilylation of olefins catalyzed by Cp2TiCl2/Sm (Cp = cyclopentadienyl) under solvent free conditions have been investigated. By using Cp2TiCl2/Sm as catalyst system, β-adducts and hydrogenation products were detected. Hydrosilylation of olefins catalyzed by Cp2TiCl2/LiAlH4 under room temperature has also been studied. The influence of TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) on Cp2TiCl2/Sm and Cp2TiCl2/LiAlH4, respectively, indicated that hydrosilylation of olefins catalyzed with Cp2TiCl2/Sm went through a free radical reaction pathway while a coordination mechanism was applied for Cp2TiCl2/LiAlH4 catalyst system.

Anti-Markovnikov terminal and gem-olefin hydrosilylation using a κ4-diimine nickel catalyst: selectivity for alkene hydrosilylation over ether C-O bond cleavage

The phosphine-substituted α-diimine Ni precursor, (Ph2PPrDI)Ni, has been found to catalyze alkene hydrosilylation in the presence of Ph2SiH2 with turnover frequencies of up to 124 h?1 at 25 °C (990 h?1 at 60 °C). Moreover, the selective hydrosilylation of allylic and vinylic ethers has been demonstrated, even though (Ph2PPrDI)Ni is known to catalyze allyl ester C-O bond hydrosilylation. At 70 °C, this catalyst has been found to mediate the hydrosilylation of ten different gem-olefins, with turnover numbers of up to 740 under neat conditions. Prior and current mechanistic observations suggest that alkene hydrosilylation takes place though a Chalk-Harrod mechanism following phosphine donor dissociation.

Photo-initiation hydrosilylation reaction method

The invention discloses a photo-initiation hydrosilylation reaction method, and relates to a method for hydrosilylation. The method comprises the following steps: (1) using olefin and hydrogen-containing silane as reaction raw materials, or using vinyl polysiloxane and hydrogen-containing polysiloxane as reaction raw materials; and (2) performing a hydrosilylation reaction on the reaction raw materials under illumination conditions and under the action of a photo-initiation catalyst, wherein the photoinitiator is an aroylphosphine oxide compound, a co-initiator catalyst is also included in thephoto-initiation hydrosilylation reaction method, the co-initiator is cuprous halide, and the molar ratio of the haloaroylphosphine oxide compound to the cuprous halide is (1:0.01)-(1:1); and the light source for the illumination condition is ultraviolet light, and the molar ratio of olefinic bonds in the olefin or vinyl silicone oil to the aroylphosphine oxide compound is (400:1)-(100:1). Through the method, use of precious metal catalysts is avoided, the reaction conditions are mild, the system needs no heating, and reduction of energy consumption is facilitated; and the method has good universality of the reaction substrate, and the catalytic system has a wide source and easy storage.

Tuning the redox non-innocence of a phenalenyl ligand toward efficient nickel-assisted catalytic hydrosilylation

In this report, a ligand-redox assisted catalytic hydrosilylation has been investigated. A phenalenyl ligand coordinated nickel complex has been utilized as an electron reservoir to develop a base metal-assisted catalyst, which very efficiently hydrosilylates a wide variety of olefin substrates under ambient conditions. A mechanistic investigation revealed that a two-electron reduced phenalenyl based biradical nickel complex plays the key role in such catalysis. The electronic structure of the catalytically active biradical species has been interrogated using EPR spectroscopy, magnetic susceptibility measurements, and electronic structure calculations using a DFT method. Inhibition of the reaction by a radical quencher, as well as the mass spectrometric detection of two intermediates along the catalytic loop, suggest that a single electron transfer from the ligand backbone initiates the catalysis. The strategy of utilising the redox reservoir property of the ligand ensures that the nickel is not promoted to an unfavorable oxidation state, and the fine tuning between the ligand and metal redox orbitals elicits smooth catalysis.