Air-initiated hydrosilylation of unactivated alkynes and alkenes and dehalogenation of halohydrocarbons by tris(trimethylsilyl)silane under solvent-free conditions
A highly efficient air-initiated hydrosilylation of unactivated alkynes and alkenes and dehalogenation of halohydrocarbons with tris(trimethylsilyl)silane ((TMS)3SiH) as a reducing agent has been established under solvent-free conditions. These observations demonstrate that the potential and versatility of air to function as a competent initiator for Si–H bond activations. It can rival organic initiators
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.
Oxime ester-enabled anti-Markovnikov hydrosilylation of alkenes
作者:Guo Shen、Shaomin Fu、Bo Liu
DOI:10.1039/d2cc03917f
日期:——
An oxime ester-enabled anti-Markovnikov hydrosilylation of alkenes is developed.