Light-Promoted Arylsilylation of Alkenes with Hydrosilanes

Abstract

Herein, we report light-promoted photo/hydrogen atom transfer dual catalysis for arylsilylation of alkenes via the radical−radical cross-coupling with diverse hydrosilanes, which provides a simple and efficient method to prepare various organosilicon compounds with a wide range of substrate scope and good functional group tolerance under transition-metal-and chemical-oxidant-free conditions. Furthermore, the arylsilylation of alkenes can also proceed via the possible electron donor− acceptor complex under exogenous photocatalyst-free conditions.

Organoelectrophotocatalytic C–H Silylation of Heteroarenes

“…The peroxide-promoted (such as DTBP, TBHP, LPO, and DCP) and Mn-catalyzed approaches for the generation of silyl radicals at high temperatures have been explored. In addition, the photochemical transforms of silyl radicals can also be achieved by using a multicatalytic system including a photocatalyst, a HAT reagent, or an oxidant …”

Base-mediated C–B bond activation of benzylic boronate for the rapid construction of β-silyl/boryl functionalized 1,1-diarylalkanes from aromatic alkenes

“…As exemplified in Scheme 4, the scope is striking because both C(sp 2 )- and C(sp 3 )-hybridized electrophiles, including aryl cyanide, aryl chloride, alkyl chloride, and alkyl bromides, could be employed. Using styrene as the model substrate, most of the cyano-substituted pyridines are effective coupling partners, in spite of the electronic and substituent effects of the cyano group at the C-2, C-3, C-4 positions ( 33–54 ) and clearly illustrate the true complementary nature of this method to Minisci-type reactions 18 or radical based ipso -substitution of pyridine nitriles 19,20 given that a challenging C-3 substituted product is also accessible ( 48 ). More importantly, other aryl (or azines) cyanides, including 2 or 4-cyanoquinoline, 1-cyano-isoquinoline, 1,4- or 1,2-dicyanobenzene, 4-cyanobiphenyl, and even benzonitrile were also allowed in the reaction, providing the desired products 49–55 in moderate to good yields.…”

Radical Decyanations of Unactivated Carbon‐CN Bonds: Recent Achievements and Mechanistic Studies

“…For similar alkene difunctionalization reactions, [101] photo-induced multicomponent bifunctionalization of unactivated alkenes were also developed through decyanative strategy by the Lin group [102] and Deng group, [103] respectively (Scheme 29). In Lin's work, arylsilylation of alkenes under a transition-metal free with visible-light irradiation was realized by photoredox and HAT catalysis, this methodology offered a rapid strategy to silicon-containing complex compounds with wide substrate scope and good functional group tolerance.…”