17718-70-6

Upstream product

• 37160-45-5 bis(2-oxo-2-phenyl-ethyl)mercury 
• 4149-29-5 bis(triethylsilyl)mercury 
• 617-86-7 triethylsilane 
• 98-86-2 acetophenone 
• 79271-56-0 triethylsilyl trifluoromethyl sulfonate 
• 93-97-0 benzoic acid anhydride 
• 994-30-9 triethylsilyl chloride 
• 70-11-1 α-bromoacetophenone 

Downstream Products

• 145624-52-8 (R)-3-(2-furyl)-3-hydroxy-1-phenylpropan-1-one 
• 1144528-47-1 (S)-3-(2-furyl)-3-hydroxy-1-phenylpropan-1-one 
• 42052-51-7 3-hydroxy-1,3-diphenylpropan-1-one 
• 16206-34-1 3‐methyl‐2,5‐diphenyl‐1H‐pyrrole 

Relevant academic research and scientific papers

FLP-Catalyzed Transfer Hydrogenation of Silyl Enol Ethers

Herein we report the first catalytic transfer hydrogenation of silyl enol ethers. This metal free approach employs tris(pentafluorophenyl)borane and 2,2,6,6-tetramethylpiperidine (TMP) as a commercially available FLP catalyst system and naturally occurring γ-terpinene as a dihydrogen surrogate. A variety of silyl enol ethers undergo efficient hydrogenation, with the reduced products isolated in excellent yields (29 examples, 82 % average yield).

Transition metal-catalyzed dehydrogenative silylation of ketones with amine and halide as cocatalysts

It was found that dehydrogenative silylation of ketones with hydrosilanes proceeds in the presence of a transition metal catalyst such as palladium on carbon or iridium carbonyl, with amine and halide as cocatalysts, to give the corresponding silyl enol e

Neutral-Eosin-Y-Photocatalyzed Silane Chlorination Using Dichloromethane

Chlorosilanes are versatile reagents in organic synthesis and material science. A mild pathway is now reported for the quantitative conversion of hydrosilanes to silyl chlorides under visible-light irradiation using neutral eosin Y as a hydrogen-atom-transfer photocatalyst and dichloromethane as a chlorinating agent. Stepwise chlorination of di- and trihydrosilanes was achieved in a highly selective fashion assisted by continuous-flow micro-tubing reactors. The ability to access silyl radicals using photocatalytic Si?H activation promoted by eosin Y offers new perspectives for the synthesis of valuable silicon reagents in a convenient and green manner.

Palladium-Catalyzed α-Arylation of Silylenol Ethers in the Synthesis of Isoquinolines and Phenanthridines

A diverse array of isoquinolines and phenanthridines have been accessed by developing a two-step, one-pot method constituting regioselective palladium-catalyzed Kuwajima-Urabe α-arylation of silylenol ethers and acid-mediated deprotection, annulation, and aromatization. Structural diversity in the silylenol ethers leads to three different classes of isoquinolines and phenanthridines from which related natural products can be derived. The synthetic utility of this method by the quick assembly of the natural product trispheridine is also demonstrated.

Rhodium-Catalyzed Dehydrogenative Silylation of Acetophenone Derivatives: Formation of Silyl Enol Ethers versus Silyl Ethers

A series of rhodium–NSiN complexes (NSiN=bis (pyridine-2-yloxy)methylsilyl fac-coordinated) is reported, including the solid-state structures of [Rh(H)(Cl)(NSiN)(PCy3)] (Cy=cyclohexane) and [Rh(H)(CF3SO3)(NSiN)(coe)] (coe=cis-cyclooctene). The [Rh(H)(CF3SO3)(NSiN)(coe)]-catalyzed reaction of acetophenone with silanes performed in an open system was studied. Interestingly, in most of the cases the formation of the corresponding silyl enol ether as major reaction product was observed. However, when the catalytic reactions were performed in closed systems, formation of the corresponding silyl ether was favored. Moreover, theoretical calculations on the reaction of [Rh(H)(CF3SO3)(NSiN)(coe)] with HSiMe3and acetophenone showed that formation of the silyl enol ether is kinetically favored, while the silyl ether is the thermodynamic product. The dehydrogenative silylation entails heterolytic cleavage of the Si?H bond by a metal–ligand cooperative mechanism as the rate-determining step. Silyl transfer from a coordinated trimethylsilyltriflate molecule to the acetophenone followed by proton transfer from the activated acetophenone to the hydride ligand results in the formation of H2and the corresponding silyl enol ether.

Synthesis of silyl monoperoxyketals by regioselective cobalt-catalyzed peroxidation of silyl enol ethers: Application to the synthesis of 1,2-dioxolanes

The cobalt-catalyzed peroxidation of silyl enol ethers with molecular oxygen and triethylsilane provided silyl monoperoxyketals in 54%-96% yield. These compounds serve as precursors to peroxycarbenium ions, which undergo annulations to provide 1,2-dioxola

Chemoselective silyl transfer in the Mukaiyama aldol reaction promoted by super silyl Lewis acid

In the silyl Lewis acid-promoted Mukaiyama aldol reaction, the steric and electronic properties of the silyl group on the silyl Lewis acid influence the reaction mechanism and product distribution. When super silyl triflates such as (TMS)3SiOTf and (TES)3SiOTf are used as Lewis acids, the silyl group of the silyl enol ether chemoselectively transfers to the product. The mechanistic details have been investigated using density functional theory (DFT) calculations.

Insight into the mechanism of carbonyl hydrosilylation catalyzed by brookharts cationic iridium(iii) pincer complex

New experimental findings suggest partial revision of the currently accepted mechanism of the carbonyl hydrosilylation catalyzed by the iridium(III) pincer complex introduced by Brookhart. Employing silicon-stereogenic silanes as a stereochemical probe results in racemization rather than inversion of the configuration at the silicon atom. The degree of the racemization is, however, affected by the silane/carbonyl compound ratio, and inversion is seen with excess silane. Independently preparing the silylcarboxonium ion intermediate and testing its reactivity then helped to rationalize that effect. The stereochemical analysis together with these control experiments, rigorous multinuclear NMR analysis, and quantum-chemical calculations clearly prove that another silane molecule participates in the hydride transfer. The activating role of the silane is unexpected but, in fact, vital for the catalytic cycle to close.

Enantioselective Mukaiyama-Michael reaction of silyl enol ethers to 2-enoylpyridine N-oxides catalyzed by copper-bis(oxazoline) complex

A catalytic enantioselective Mukaiyama-Michael reaction of 2-enoylpyridine N-oxides has been developed using a simple bis(oxazoline)-copper complex. A variety of silyl enol ethers undergo smooth Michael addition with 2-enoylpyridine N-oxides to furnish the corresponding Michael adducts in high yields with high enantioselectivities (up to 97% ee).

Base-free dehydrogenative coupling of enolizable carbonyl compounds with silanes

A dehydrogenative coupling between enolizable carbonyl compounds and equimolar amounts of triorganosilanes catalyzed by a tethered ruthenium complex with a Ru-S bond is reported. The complex is assumed to fulfill a dual role by activating the Si-H bond to release a silicon electrophile and by abstracting an α-proton from the intermediate silylcarboxonium ion, only liberating dihydrogen as the sole byproduct. Reaction rates are exceedingly high at room temperature with very low loadings of the ruthenium catalyst.