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

Abstract

This Concept shows the flexibility and applicability of (Me3Si)3SiH in several synthetic transformations, such as radical reductions, consecutive radical reactions and hydrosilylation. The reactivity of (Me3Si)3SiH combines the multidisciplinary aspects of physical organic chemistry and organic synthesis, extending to polymers and materials science, as in the functionalization of flat silicon surfaces.

Radical 1,2‐O→C Transposition for Conversion of Phenols into Benzoates by O‐Neophyl Rearrangement/Fragmentation Cascade

“…Only traces of the desired product (D) were detected by 1 H NMR spectroscopy and GC, even after heating at 135 8C in a sealed tube, with very low conversion of starting material. However, when the reaction was performed using triethylsilane (TES) [11] and di-tert-butyl peroxide (TOOT) at 135 8C in benzene, the proposed O!C transposition cascade indeed proceeded to afford 59 % of phenyl benzoate.…”

Application of Germyldesulfonylation Reactions to the Synthesis of Germanium-Containing Nucleoside Analogues

“…It is noteworthy that contrary to the stannyldesulfonylation reactions,3,6 the germyldesulfonylations of the vinyl sulfones derived from the sugar modified nucleosides are stereoselective since the corresponding ( Z )-isomers of vinyl germanes 7 or 8 were not isolated from the crude reaction mixtures. Germyldesulfonylation reactions presumably occurred via the radical addition-elimination mechanism in analogy to the silyl- and stannyldesulfonylation processes 1,18,26…”

Synthesis and characterisation of two new binaphthyl trisilanes

“…The use of silanes as alternatives to tributyltin hydride in radical chemistry is also growing in popularity, driven by their lower toxicity, ease of separation from products and often greater selectivity [2]. Particularly of note are tris(trimethylsilyl)silane 1 and related trisilanes such as 2, developed by Chatgilialoglu and coworkers [3,4].…”