135746-52-0

Upstream product

• 135746-51-9 5-chloro-1-(methyldiphenylsilyl)pentan-1-one 
• 882882-27-1 [(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)dichloromethyl]methyldiphenylsilane 
• 693-03-8 n-butyl magnesium bromide 
• 144-79-6 chloromethyldiphenylsilane 
• 383180-56-1 dichlorobis(methyldiphenylsilyl)methane 

Relevant academic research and scientific papers

Oxidation of gem-borylsilylalkylcoppers to acylsilanes with air

1-Boryl-1-silylalkylcoppers react with molecular oxygen in the presence of pyridine to afford acylsilanes efficiently. The one-pot process consists of two reactions: alkylation of 1-boryl-1-chloro-silylmethyllithium with Grignard reagents in the presence of copper(I) cyanide and aerobic oxidation of the alkylcopper species. This procedure enables us to access the divergent synthesis of acylsilanes.

Preparation of α-silyl- or α,α-bis(silyl)-substituted alkylcopper reagents and their synthetic use

Treatment of chlorobis(methyldiphenylsilyl)methyllithium with various alkyl and aryl Grignard reagents and CuCN·2LiCl afforded 1,1- disilylalkylcopper species. The aerobic oxidation of the resulting copper reagents provided a variety of acylsilanes in good yields. Meanwhile, treatment of dichloro(methyldiphenylsilyl)methyllithum with Bu2CuLi·LiCN provided 1-cyano-1-silylalkylcopper species via consecutive double 1,2-migration of alkyl and cyano groups.

Intramolecular free radical cyclizations using acylsilanes as radicalphiles

Carbon radicals add intramolecularly to acylsilanes at the carbonyl carbon followed by radical Brook rearrangement to give silylated cyclopentanols or cyclohexanols in good yields.