Ethers silylcarbonylation

When substituted silanes are used instead of hydrogen, the process is referred to as silylformylation or silylcarbonylation. Only rhodium complexes catalyze the transformation of unsaturated compounds to silylaldehydes via the silylformylation reaction. Iridium complexes also are able to catalyze the simultaneous incorporation of substituted silanes and CO into unsaturated compounds, although during the reaction other types of product are formed. In the presence of [ IrCl(C03) ] and [Ir4(CO)i2]) the alkenes react with trisubstituted silanes and CO to give enol silyl ethers of acyl silanes [58] according to Scheme 14.10. 

The silylcarbonylation of alkenes catalyzed by Co2(CO)s giving homologous silyl enol ethers was reported by Murai and coworkers in 1977 as a silicon version of hydro-formylation of alkenes, and developed as a unique synthetic method302-304. Although... 

The 1,3-silyl migrations from O to C in lithiated silyl enol ethers 205 afforded a-silylcarbonyl compounds 206 after hydrolysis (equation 134)326 -330. 

Silylcarbonylation is a known term describing formally the silicon version of hydroformylation (cf. Section 2.1.1) discovered by Collenille [147] and later developed by Murai and co-workers, in which hydrogen is replaced by trialkylsilane, eq. (10) [148]. The silylformylation of alkenes is catalyzed by Co2(CO)g [148], [RhCl(CO)2]2 [149], RhCl(PPh3)3 [150], Ru3(CO)i2, and HRujfCO),- [151] to give silyl enol ethers of the homologous aldehydes as the sole products. 

Rh catalyses the hydrosilylation of alkenes and the dehydrogenative silylation of 1,5-dienes and alkynes, and the silylcarbonylation of alkynes to give p-silylacrylaldehydes with exceptional stereocontrol , ketones and enones give silyl enol ethers, 1,3-cyclobutane dione gives 3-hydroxycyclobutanone, and assists in the silylformylation of ethynyl pyirolidone derivatives to give pyrrolizidine alkaloids, and epoxides to give p-siloxy aldehydes, and... 

Cft 8H3 gOftP2ReSi, fac-(1,2-Bis(diphenylphosphino)ethane)(triphenyl-silylcarbonyl)tricarbonylrhenium, 43B, 1028 CftsHft6P2U2 0.5 CftHioOf Tetrakis(r -cyclopentadienyl)bis[M (methylene (diphenylphosphino)methylidyne) ]-diuranium diethyl ether solvate, 46B, 829... 

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