205994-51-0Relevant academic research and scientific papers
Intramolecular Homolytic Substitution Enabled by Photoredox Catalysis: Sulfur, Phosphorus, and Silicon Heterocycle Synthesis from Aryl Halides
Garrido-Castro, Alberto F.,Salaverri, Noelia,Maestro, M. Carmen,Alemán, José
supporting information, p. 5295 - 5300 (2019/07/03)
Aryl radical generation and manipulation constitutes a long-standing challenge in organic synthesis. Photocatalytic single-electron reduction of aryl halides has been established as a premier activation pathway to reach these intermediates. The current st
The S(H)i reaction at silicon - A new entry into cyclic alkoxysilanes
Studer, Armido,Steen, Hanno
, p. 759 - 773 (2007/10/03)
A new mild radical method for the preparation of cyclic five-membered alkoxysilanes is reported. This method comprises an intramolecular homolytic substitution reaction at silicon (S(H)i). Various leaving groups (SiMe3, GeMe3, SnMe3) were tested in the homolytic substitution reaction. We found that high yields were only obtained for silanes bearing a trimethyl-stannyl functionality as leaving group in the S(H)i reaction. Rate constants for the cyclization reaction were estimated by conducting standard competition experiments. Based on the kinetic data, more elaborate reaction sequences such as radical addition reactions with a subsequent S(H)i step were carried out. Stereoselective cyclization reactions were also investigated. Excellent 1,2 diastereoselectivities were observed. The products of the S(H)i reaction, cyclic alkoxysilanes, can easily be converted to the corresponding diol derivatives by Tamao-Fleming oxidation as demonstrated for several examples.
