42451-53-6

Upstream product

• 617-86-7 triethylsilane 
• 119-61-9 benzophenone 
• 994-30-9 triethylsilyl chloride 
• 18406-24-1 1-(triethylsilyloxy)-4-methoxybenzene 
• 91-01-0 1,1-Diphenylmethanol 
• 18296-01-0 triethylsilyl formate 
• 134-85-0 4-chlorobenzophenone 

Downstream Products

• 6328-61-6 trimethylsilyldiphenylmethane 
• 91-01-0 1,1-Diphenylmethanol 

Relevant academic research and scientific papers

An N-Heterocyclic Carbene with a Saturated Backbone and Spatially-Defined Steric Impact

The synthesis and coordination chemistry of a saturated analogue of a “bulky-yet-flexible” N-heterocyclic carbene (NHC) ligand are described. “SIPaul” is a 4,5-dihydroimidazol-2-ylidene ligand with unsymmetrical aryl N-substituents, and is one of the grow

Phosphirenium ions as masked phosphenium Catalysts: Mechanistic evaluation and application in synthesis

The utilization of phosphirenium ions is presented; optimized and broadened three-membered ring construction is described together with the use of these ions as efficient pre-catalysts for metal-free carbonyl reduction with silanes. Full characterization of the phosphirenium ions is presented, and initial experimental and computational mechanistic studies indicate that these act as a "masked phosphenium"source that is accessed via ring opening. Catalysis proceeds via associative transfer of {Ph2P+} to a carbonyl nucleophile, Ha'SiR3 bond addition over the C=O group, and associative displacement of the product by a further equivalent of the carbonyl substrate, which completes the catalytic cycle. A competing off-cycle process leading to vinyl phosphine formation is detailed for the hydrosilylation of benzophenone for which an inverse order in [silane] is observed. Experimentally, the formation of side products, including off-cycle vinyl phosphine, is favored by electrondonating substituents on the phosphirenium cation, while catalytic hydrosilylation is promoted by electron-withdrawing substituents. These observations are rationalized in parallel computational studies.

Reversible Silylium Transfer between P-H and Si-H Donors

The Mo=PR2 π* orbital in a Mo phosphenium complex acts as acceptor in a new PIII-based Lewis superacid. This Lewis acid (LA) participates in electrophilic Si-H abstraction from E3SiH to give a Mo-bound secondary phosphine ligand, Mo-PR2H. The resulting Et3Si+ ion remains associated with the Mo complex, stabilized by η1-P-H donation, yet undergoes rapid exchange with an η1-Si-H adduct of free silane in solution. The equilibrium between these two adducts presents an opportunity to assess the role of this new LA in catalytic reactions of silanes: is the LA acting as a catalyst or as an initiator? Preliminary results suggest that a cycle including the Mo-bound phosphine-silylium adduct dominates in the catalytic hydrosilylation of acetophenone, relative to a putative cycle involving the silane-silylium adduct or “free” silylium.

Hydrosilylation of Carbonyls Catalyzed by Hydridoborenium Borate Salts: Lewis Acid Activation and Anion Mediated Pathways

The electronically unsaturated three-coordinated hydridoborenium cations [LBH]+[HB(C6F5)3]-(1) and [LBH]+[B(C6F5)4]-(2), supported by a bis(phosphinimino)amide ligand, were found to be excellent catalysts for hydrosilylation of a range of aliphatic and ar

Electrophilic Organobismuth Dication Catalyzes Carbonyl Hydrosilylation

Bismuth compounds are gaining importance as potential alternatives to transition-metal complexes and electron deficient lighter p-block compounds in homogeneous catalysis. Computational analysis on the two-coordinate [(Me2NC6H4)Bi]2+ possessing three electrophilic sites is experimentally evidenced by the isolation of [{Me2NC6H4}Bi{OP(NMe2)3}3][B(3,5-C6H3Cl2)4]2. These observations led us to generate dicationic organobismuth catalyst, [(Me2NC6H4)Bi(L)3]2+ (L=aldehyde/ketone), evidenced by NMR spectroscopy in solution and by single-crystal X-ray diffraction in the solid state. It efficiently catalyzes hydrosilylation of aldehydes and ketones resulting in silyl ethers as the only products in high yields. Our investigations support a carbonyl activation mechanism at the bismuth center followed by Si?H addition.

+: A Masked Potent Boron Lewis Acid

The chemistry of the boron cation has been revitalized in the past decade due to its newfound application in stoichiometric and catalytic organic reactions. To extend the frontier of boron cation catalysis, we came to discover that a mesityl-substituted η5-Cp*-coordinated boron cation could serve as a powerful Lewis acid for organic catalytic transformations. The boron cation [Cp*B-Mes][B(C6F5)4] ([1][B(C6F5)4]) stabilized in a boronium-like electronic structure binds to Et3PO readily and displays an acceptor number exceeding that of B(C6F5)3 on the Gutmann-Beckett acidity scale. The steric and electronic stabilization exerted by the electron-donating Cp? renders the highly Lewis acidic boron cation an easy-to-handle catalyst for hydrodeoxygenation of aryl ketones at ambient temperature. The exceptional catalytic performance of [1]+ implies that the incorporation of a coordinatively flexible substituent at boron is critical in bringing catalytic activity and stability to boron cation catalysts.

Organoaluminum cations for carbonyl activation

In search of stable, yet reactive aluminum Lewis acids, we have isolated an organoaluminum cation, [(Me2NC6H4)2Al(C4H8O)2]+, coordinated with two labile tetrahydrofuran ligands. Its catalytic performance in aldehyde dimerization reveals turn-over frequencies reaching up to 6000 h-1, exceeding that of the reported main group catalysts. The cation is further demonstrated to catalyze hydroelementation of ketones. Mechanistic investigations reveal that aldehyde dimerization and ketone hydrosilylation occur through carbonyl activation.

Silylative Pinacol Coupling Catalyzed by Nitrogen-Doped Carbon-Encapsulated Nickel/Cobalt Nanoparticles: Evidence for a Silyl Radical Pathway

The silylative pinacol coupling of arylaldehydes catalyzed by an easily accessible, heterogeneous base-metal catalyst is demonstrated. Instead of using the classical combination of catalyst, stoichiometric metal reductants, and chlorosilanes, the develope

A Versatile Iridium(III) Metallacycle Catalyst for the Effective Hydrosilylation of Carbonyl and Carboxylic Acid Derivatives

A versatile iridium(III) metallacycle catalysed rapidly and selectively the reduction of a large array of challenging esters and carboxylic acids as well as various ketones and aldehydes. The reactions proceeded in high yields at room temperature by hydrosilylation followed by desilylation. Although the reactions of various aldehydes and ketones resulted exclusively in alcohols, the hydrosilylation of esters led to alcohols or ethers, depending on the type of substrate. Regarding the carboxylic acids, again the nature of the reagent controlled the outcome of the hydrosilylation reaction, either alcohols or aldehydes being formed.

Iridacycles as Catalysts for the Autotandem Conversion of Nitriles into Amines by Hydrosilylation: Experimental Investigation and Scope

The set of iridacycles [{C,N}Cp?IrIII-Cl] ({C,N} = benzo[h]quinoline, dibenzo[f,h]quinoline) containing the (pentamethylcyclopentadienyl)iridium(III) unit were synthesized and derivatized into cations [{C,N}Cp?Ir-NCMe]+ associated wi