18666-34-7

Upstream product

• 33935-31-8 chloro(N,N-diethylamino)diphenylsilane 
• 3839-31-4 dimethyl(phenyl)silyllithium 
• 184678-40-8 1-dimethylamino-1,1,2-triphenyl-2,2-trimethyldisilane 
• 80-10-4 diphenylsilyl dichloride 

Downstream Products

• 150043-00-8 C₂₇H₃₄OSi₂ 
• 150043-67-7 1,1-Dimethyl-2-(1-methyl-pent-4-enyl)-1,2,2-triphenyl-disilane 
• 150042-93-6 C₂₅H₃₀OSi₂ 
• 150042-96-9 C₂₅H₃₀OSi₂ 
• 150043-86-0 1,1-Dimethyl-2-(1-methyl-but-3-enyl)-1,2,2-triphenyl-disilane 
• 259213-81-5 C₃₆H₅₀O₃Si₂ 
• 150043-85-9 1,1-Dimethyl-2-(2-methyl-but-3-enyl)-1,2,2-triphenyl-disilane 
• 150043-66-6 1,1-Dimethyl-2-(2-methyl-pent-4-enyl)-1,2,2-triphenyl-disilane 
• 150043-65-5 1,1-Dimethyl-2-(3-methyl-pent-4-enyl)-1,2,2-triphenyl-disilane 
• 857286-62-5 C₂₉H₃₈OSi₂ 
• 857286-80-7 C₂₉H₃₈OSi₂ 
• 175982-51-1 C₃₀H₄₀OSi₂ 
• 857286-76-1 C₂₉H₃₆OSi₂ 
• 175982-54-4 C₃₀H₃₂OSi₂ 

Relevant academic research and scientific papers

Stereoselective radical aryl migration from silicon to carbon

Highly diastereoselective radical 1,5 phenyl migration reactions from silicon in diarylsilyl ethers to various C-centered radicals to form the corresponding 3-phenylated alcohols are described. Functionalized aryl groups can also be transferred. The effect of the variation of the attacking radical on the aryl transfer reaction is discussed. Best results are obtained for the phenyl migration to nucleophilic secondary alkyl radicals, where high yields (up to 81%) and high selectivities (up to 95% ds) have been obtained. The mechanism of the process is discussed and a model to explain the stereochemical outcome of the reaction is presented. Finally, stereoselective 1,4 aryl migration reactions from Si to C, including a new method for the α- arylation of esters, are presented.

Stereoselective intramolecular bis-silylation of alkenes promoted by a palladium-isocyanide catalyst leading to polyol synthesis

Details of a study on the intramolecular bis-silylation of terminal alkenes promoted by a palladium-tert-alkyl isocyanide catalyst are described. With a disilanyl ether derived from a homoallylic alcohol, intramolecular regioselective addition of the Si-Si linkage to the C=C bond took place to furnish an exo-ring closure product, i.e., 1,2-oxasilolane. The bis-silylation of alkenes having substituents α to the C=C bond gave trans-3,4-disubstituted oxasilolanes, while substitution β to the C=C bond favored cis-3,5-disubstituted oxasilolanes. The stereoselectivity trends are formulated as arising from a preference for a chairlike transition state over a boatlike one. A substituent, either a or β to the C=C bond, prefers the equatorial position in a chairlike transition state. The 1,2-oxasilolanes thus produced stereoselectively were oxidatively converted to the corresponding 1,2,4-triols. The present methodology for the synthesis of 1,2,4-triols was successfully extended to the stereoselective synthesis of 1,2,4,5,7- and 1,2,4,6,7-pentaols through a sequence of intramolecular bis-silylations. The bis-silylation was also performed with alkenes linked to disilanyl groups through a three-carbon chain and through an amide linkage. Stereoselections analogous to those of the ether substrates were observed. Alkenes tethered to disilanyl groups through chains of two atoms underwent similar intramolecular bissilylation. In conclusion, the intramolecular bis-silylation of C=C bonds followed by oxidation constitutes a new synthetic transformation equivalent to the stereoselective dihydroxylation of olefins.