Acyl Polysilanes: New Acyl Anion Equivalents for Additions to Electron-Deficient Alkenes

Abstract

Silenes, generated through thermolysis of acylpolysilanes, add to alpha,beta-unsaturated esters to form cyclobutanes and silylsubstituted cyclopropanes in moderate yields. Upon Si-C bond oxidation the cyclopropanes are converted directly to 1,4-dicarbonyl compounds, thus demonstrating the formal acyl anion chemistry of acyl polysilanes.

Reactivity of a Polar Silene toward Terminal Alkynes: Preference for C−H Insertion over Cycloaddition

“…Since the pioneering work of Gusel’nikov and Flowers in 1967, silene (R 2 SiCR 2 ) chemistry has matured significantly; much is now known regarding the properties and reactivity of these fundamentally important compounds, and applications of silene chemistry are now being developed. For example, silenes have been used as monomers in the synthesis of new inorganic polymers and as reagents in organic synthesis . To take full advantage of the chemistry of silenes, it is necessary to gain a better understanding of the scope and mechanisms of the reactions of silenes.…”