Electrochemical oxidation of organosilicon compounds. Part 7. The origin of .beta.-silicon effect in electron-transfer reactions of silicon-substituted heteroatom compounds. Electrochemical and theoretical studies

Basic Concepts of “Cation Pool” and “Cation Flow” Methods and Their Applications in Conventional and Combinatorial Organic Synthesis

“…The concept of electroauxiliary [11] is quite powerful to solve these problems. The pre-introduction of a silyl group [12] as an electroauxiliary decreases the oxidation potential of dialkyl ethers by virtue of orbital interaction. The interaction of the nonbonding p orbital (lone pair) of the oxygen with the CÀSi s orbital raises the HOMO level, which in turn favors the electron transfer.…”

Aminomethylation of Aryl Halides Using α-Silylamines Enabled by Ni/Photoredox Dual Catalysis

“…The carbamate 2f failed to give any observable product when using the standard conditions. This may relate to its known higher oxidation potentials, 16 although only trace product was observed when using a more oxidizing photo-catalyst such as [Ir{dFCF 3 ppy} 2 (bpy)]PF 6 . Finally, performing aminomethylation on a larger scale proved viable (5 mmol, 10-fold increase) for both the trimethylsilyl as well as the dimethylphenyl derivatives without compromising yield ( 3a , 3a’ ).…”

Preparation of sila-functional 3-sila-1-thiacyclohexanes

“…(Chloromethyl)allylmethylphenylsilane (2) was prepared by a modified procedure [15]. (Chloromethyl)methylphenylchlorosilane (1) (25.10 g, 0.12 mol) in Et 2 O (40 mL) was added to a vigorously stirred Grignard reagent, prepared from allyl chloride (13.01 g, 0.17 mol), magnesium powder (4.09 g, 0.17 g-a) in Et 2 O (20 mL) at 0°C.…”