Recent advances in photo- and electro-enabled radical silylation

Abstract

Given the rapid development of photocatalysis and electrocatalysis technology, and the importance of organosilicon compounds in the fields of materials science, synthetic chemistry, and agrochemistry, the photo- and electro-enabled radical...

General Concepts and Recent Advances in the Electrochemical Transformation of Chloro‐ and Hydrosilanes

“…Recent studies show a possible hydrosilylation of alkynes via the electrochemical reaction pathway [167] . However, the oxidation of Si−B bonds is beyond the scope of our review and has been already discussed elsewhere [35] …”

An unusualtrans-hydrosilylation of prochiral 1,1-disubstituted cyclopropenes revealing the different nature of asymmetric palladium and rhodium catalysis

“…Hydrosilylation is an extremely important and atom-economical chemical transformation in manufacturing organosilicon materials and fine chemical synthesis, both in laboratory research and in large-scale industrial applications. 1 In the past few decades, a number of catalyst systems, including transition-metals, 2 rare earth metal complexes, 3 main-group metal catalysts, 4 and photocatalyst systems, 5 have been used in hydrosilylations through a range of silicon–hydrogen bond activation pathways, 6 expressed as single-electron processes or σ-bond metathesis, 7 2-electron metal-centered redox chemistry, 8 or Lewis acid site-involved hydride abstraction reactions. 9 In particular, inspired by the success of Karstedt's and Speier's catalysts which are the most commercially used complexes of platinum, transition-metal-catalyzed hydrosilylation has garnered tremendous attention in the last decade.…”

Photocatalytic C–Si Bond Formations Using Pentacoordinate Silylsilicates as Silyl Radical Precursors: Synthetic Tricks Using Old Reagents

“…2 Notably, this strategy has been extended to the formation of a C−Si bond, where a silyl radical is generated in situ under green and mild conditions, which allows the subsequent introduction of a silyl group into a carbon skeleton with a high level of regiocontrol. 3 For example, in 2017, a visible-lightinduced photocatalytic hydrosilylation of alkenes was introduced by the Wu group, where hydrosilanes were employed to produce silyl radicals via an elegant hydrogen atom transfer (HAT) mechanism. 4 Along this line, various photocatalytic C−Si formation reactions have been disclosed for the construction of valuable silicon-containing architectures (Scheme 1a).…”