1025-08-7

Upstream product

• 3027-21-2 dimethoxy(methyl)phenylsilane 
• 703-55-9 1-naphthylmagnesiumbromide 
• 21701-61-1 1-naphthylphenylsilane 
• 75-16-1 methylmagnesium bromide 
• 111949-29-2 (5S,6S)-5,6-dimethoxy-2-methyl-2-(1-naphthyl)-1,3-dioxa-2-silacycloheptane 
• 100-58-3 phenylmagnesium bromide 
• 3553-88-6 (-)-1-Naphthylphenylmethylmethoxysilan 
• 13132-41-7 (S)-Fluoro-methyl-naphthalen-1-yl-phenyl-silane 
• 917-64-6 methyl magnesium iodide 
• 68969-41-5 (-)-α-naphthylphenylmethyl-tert-butoxysilane 
• 17998-62-8 dichloro-α-naphthylmethylsilane 
• 35742-37-1 (S)-(-)-[(-)-menthyloxy](1-naphthyl)methylphenylsilane 
• 90-14-2 1-Iodonaphthalene 
• 766-08-5 methylphenylsilane 

Downstream Products

• 119908-52-0 (S)-(4,4-Dimethyl-penta-1,2-dienyl)-methyl-naphthalen-1-yl-phenyl-silane 
• 107487-28-5 α-naphtylphenylmethylsilyl t-butylphenylthiophosphinate 
• 107487-26-3 α-naphtylphenylmethylsilyl t-butylphenyl-phosphinate 
• 1028-62-2 (+)-(R)-methyl-(α-naphthyl)phenylsilanol 
• 1028-61-1 (-)-(S)-methyl-(α-naphthyl)phenylsilanol 
• 107487-28-5 C₂₇H₂₉OPSSi 
• 208838-28-2 (E)-3-((R)-Methyl-naphthalen-1-yl-phenyl-silanyl)-prop-2-en-1-ol 
• 68969-41-5 (-)-α-naphthylphenylmethyl-tert-butoxysilane 
• 1025-09-8 (S)-methyl(naphthalen-1-yl)phenylsilane 
• 863332-67-6 11-[(R)-methyl(1-naphthyl)phenylsilyl]-9-O-(trimethylsilyl)-10,11-dihydrocinchonidine 
• 81476-81-5 (CO)5MnSiCH₃(C₆H₅)C₁₀H₇ 
• 81476-83-7 P(C₆H₅)3(CO)4MnSiCH₃(C₆H₅)C₁₀H₇ 

Relevant academic research and scientific papers

Selective Manganese-Catalyzed Oxidation of Hydrosilanes to Silanols under Neutral Reaction Conditions

The first manganese-catalyzed oxidation of organosilanes to silanols with H2O2 under neutral reaction conditions has been accomplished. A variety of organosilanes with alkyl, aryl, alknyl, and heterocyclic substituents were tolerated, as well as sterically hindered organosilanes. The oxidation appears to proceed by a concerted process involving a manganese hydroperoxide species. Featuring mild reaction conditions, fast oxidation, and no waste byproducts, the protocol allows a low-cost, eco-benign synthesis of both silanols and silanediols.

Borane-Catalyzed Reductive α-Silylation of Conjugated Esters and Amides Leaving Carbonyl Groups Intact

Described herein is the development of the B(C6F5)3-catalyzed hydrosilylation of α,β-unsaturated esters and amides to afford synthetically valuable α-silyl carbonyl products. The α-silylation occurs chemoselectively, thus leaving the labile carbonyl groups intact. The reaction features a broad scope of both acyclic and cyclic substrates, and the synthetic utility of the obtained α-silyl carbonyl products is also demonstrated. Mechanistic studies revealed two operative steps: fast 1,4-hydrosilylation of conjugated carbonyls and then slow silyl group migration of a silyl ether intermediate.

Palladium-catalyzed Si-C bond-forming silylation of aryl iodides with hydrosilanes: An enhanced enantioselective synthesis of silicon-stereogenic silanes by desymmetrization

An enantioselective Pd-catalyzed silicon-carbon bond-forming silylation reaction of aryl iodides with hydrosilanes for the synthesis of silicon-stereogenic silanes has been developed, in which a systematic optimization of a TADDOL-derived monodentate phos

Synthesis of optically active tertiary silanes via Pd-catalyzed enantioselective arylation of secondary silanes

We herein describe the development of an efficient enantioselective catalytic system that promotes the arylation of secondary silanes. Our method involves treatment of secondary silanes and aryl iodides with a Pd 2(dba)3-asymmetric p

Stereocontrolled synthesis of tertiary silanes via optically pure 1,3,2-oxazasilolidine derivatives

Optically pure 1,3,2-oxazasilolidine derivatives were synthesized from a chiral 1,2-amino alcohol. These heterocyclic compounds containing a stereogenic silicon atom produced tertiary silanes with excellent optical purity through successive reactions with

An efficient solvent-free route to silyl esters and silyl ethers

Dinuclear metal complexes, especially (p-cymene)ruthenium dichloride dimer {[RuCl2(p-cymene)]2}, have been found to exhibit high catalytic performance for the dehydrosilylation of various kinds of carboxylic acids and alcohols. The dehydrosilylation with [RuCl2(p-cymene)] 2 proceeded efficiently with only one equivalent of silane with respect to substrate (carboxylic acids or alcohols) under solvent-free conditions to give the corresponding silyl esters and ethers in excellent yields with a high turnover number (TON) and frequency (TOF). The 1H NMR spectrum of a toluene-d8 solution of [RuCl2(p-cymene)] 2 and a silane showed a signal assignable to the ruthenium hydride species. In contrast, no new signals were detected in the 1H NMR spectrum of a toluene-d8 solution of [RuCl2(p-cymene)] 2 and a carboxylic acid or an alcohol. There-fore, the ruthenium metal in [RuCl2(p-cymene)]2 activates a silane to afford the hydride intermediate, possibly a silylmetal hydride species. Then, the nucleophilic attack of a substrate (carboxylic acid or alcohol) to the hydride intermediate proceeds to give the corresponding silylated product. The present dehydrosilylation with an optically active silane proceeded exclusively under inversion of stereochemistry at the chiral silicon center, suggesting that the nucleophilic attack of a substrate to the hydride intermediate occurs from the backside of the ruthenium-silicon bond.

A stereoselective approach to optically active bifunctional 1,3-dimethyl-1,3-diphenyldisiloxanes

(Matrix presented) Functionalized disiloxanes have attracted much attention as versatile synthetic intermediates in the preparation of disiloxane-containing polymers. In this report, a highly stereoselective (98% inversion) halogenating cleavage reaction of the silicon-naphthyl bond to obtain optically active (S,S)-1,3-dimethyl-1,3-diphenyldisiloxanediol ((S,S):(R,S):(R,R) = 86:14:0) was demonstrated.

Highly stereoselective metathesis reaction between optically active hydrosilane and copper(I) salt in 1,3-dimethyl-2-imidazolidinone

Highly stereoselective metathesis reactions between optically active silyl compounds and copper(I) salts in 1,3-dimethyl-2-imidazolidinone (DMI) are reported. The substitution reaction of (+)-α-naphthylphenylmethylsilane with a mixture of lithium tert-butoxide and copper(I) salt smoothly proceeded in DMI to give the corresponding silyl ether with a high degree of retention of the configuration in a quantitative yield. The use of DMI as a solvent and the presence of a chloride ion are necessary for this reaction. An optically active alkynylsilane also reacted with the mixed reagent to afford the corresponding silyl ether. A mechanism of oxidative addition of the hydrosilane and reductive elimination of the silyl ether on copper is proposed.

Migration of aryl groups from silicon to carbon in α,β-epoxysilanes. A new model for hypervalent silicon study

The reaction of (2R,3R)-3-(triphenylsilyl)glycidol (1) with n-Bu4NF·3H2O in THF, followed by treatment of the product with p-nitrobenzoyl chloride yields (2S)-glycidol p-nitrobenzoate (4) and trans-cinnamyl p-nitrobenzoate (6) in a ratio of 1:1.5. The reaction of (R)Si-(2R,3R)- or (R)Si-(2S,3S)-3-[(methyl)(phenyl)(1-naphthyl)silyl]-glycidols, 7 or 8 respectively, with n-Bu4NF·3H2O affords mixtures of the respective glycidol, trans-cinnamyl alcohol and 3-(1-naphthyl)allyl alcohol. No significant difference in the product distribution in reaction of these two diasteromers was observed.

Asymmetric Synthesis of Organosilicon Compounds Using a C2 Chiral Auxiliary

Optically active silanes were synthesized by a novel asymmetric synthesis which involved the diastereoselective ring-opening reaction of 1,3-dioxa-2-silacycloheptanes bearing a C2 chiral auxiliary with Grignard reagents, followed by a lithium aluminum hydride (LiAlH4) reduction. (R)-Ethylmethylphenylsilane and (R)-methylphenylpropylsilane were derived in 93%ee and 98%ee, respectively. The preparation of the other optical silanes is also described. The maximum rotations of some of them have been determined by 1H NMR and/or capillary GC methods. A mechanism for a diastereoselective ring-opening reaction is proposed based on the stereochemical results.