Tris(trimethylsilyl)silane: an efficient hydrosilylating agent of alkenes and alkynes
摘要:
Tris(trimethylsilyl)silane adds across the double bond of a variety of mono-, di-, and trisubstituted olefins under free-radical conditions in good yields. The reaction, which proceeds via a free-radical chain mechanism, is highly regioselective (anti-Markovnikov). Addition to prochiral olefins bearing an ester group is highly stereoselective. The factors that control the stereochemistry have been discussed terms of preferred conformations of the intermediate carbon-centered radicals and are thought to be of steric origin.
Alkene Assisted Homolysis of the Si-H, Ge-H, and Sn-H Bond: New Examples of Molecule Assisted Homolysis (MAH)
作者:Ursula Biermann、Gerd Klaassen、Rainer Koch、Jürgen O. Metzger
DOI:10.1002/ejoc.201900363
日期:2019.6.16
Mix tris(trimethylsilyl) silane with an alkene, wait and isolate the hydrosilylation product in good yield. Where is the initiator? What′s doing the silane with the alkene? The Si‐H hydrogen is transferred to the alkene to give two radicals in a most slow reaction, initiating a most efficient radical chain reaction. Analogous hydrogermylation and hydrostannylation are reported as well.