Tris(trimethylsilyl)silane. A new reducing agent

A step toward polytwistane: synthesis and characterization of C2-symmetric tritwistane

“…Recrystallization from hexanes afforded crystals suitable for X-ray diffraction experiments for both compounds. .0 10,14 ]tetradecane (30). …”

“…Global dehalogenation of tetrachloro dibromo tritwistane 22 also failed under a variety of conditions. By contrast, dehalogenation of dibromo tritwistane 27 using Chatgilialoglu's reagent 14 was more successful and gave the parent hydrocarbon 3 (Scheme 5). C 2 -Symmetric tritwistane (3) was easy to identify due to its simplified 1 H-and 13 C-NMR spectra (see ESI †).…”

(Me3Si)3SiH: Twenty Years After Its Discovery as a Radical‐Based Reducing Agent

“…Tris(trimethylsilyl)silane, (Me 3 Si) 3 SiH, was synthesized by Gilman and co-workers in 1965 and was then almost totally forgotten for the next 20 years, [1] until our laboratory discovered that this material could serve as a radical-based reducing agent. The rebirth of (Me 3 Si) 3 SiH represents one example of Sleeping Beauty in chemistry!…”

Flight from the Tyranny of Tin: The Quest for Practical Radical Sources Free from Metal Encumbrances

“…This procedure, termed polarity-reversal catalysis, is also effective for hydrosilylation of alkenes using triethylsilane: [42] The most successful and widely used replacement for tin hydride is undoubtedly tris(trimethylsilyl)silane. [43,44] Not only does this reagent pose little toxic threat, but it also produces fewer by-products of direct reduction because its SiÀH bond is about 5 kcal mol À1 stronger than the SnÀH bond of tributyltin hydride. This has often enabled radical procedures to be accomplished with a stoichiometric amount of the silane in the initial reaction mixture, instead of the tedious slow-addition, high-dilution technique frequently essential with tin hydrides.…”