Recent Progress in Transition Metal‐Catalyzed Hydrosilane‐Mediated C−H Silylation

Abstract

Organosilicon compounds are widely used in materials science, medicinal chemistry and synthetic chemistry. Recently, significant progress has been achieved in transition metal‐catalyzed dehydrogenative C−H silylation. Particularly, recently developed monohydrosilane and dihydrosilane mediated C−H silylation have emerged as powerful tools in constructing C−Si bonds. Besides, dihydrosilane‐mediated enantioselective asymmetric C−H silylation has successfully enabled the construction of central and helical silicon chirality. In addition, chiral organosilicon compounds have exhibited excellent photoelectric material properties and broad application prospects. Furthermore, organosilicon compounds could under a series of functional group transformations to enrich the diversity of silicon chemistry. This review will present a comprehensive picture of the development of transition metal‐catalyzed hydrosilane‐mediated intramolecular C(sp2)−H and C(sp3)−H silylation organized by their reaction types and mechanisms. In addition, dihydrosilane‐mediated enantioselective asymmetric C−H silylation to construct central and helical silicon chirality will also be highlighted in the review.

Synthesizing Silyl Arylsulfonyl Hydrazones as Silyldiazomethane Precursors and Their Use in Rhodium‐Catalyzed Reactions

“…In contrast, hydrazone 5 m bearing a 3‐phenylpropyl group was also applicable to silacyclopentane 13 through C( sp 3 )−H functionalization (Figure 3C). These silacycle syntheses through C−C bond formation by C( sp 3 )−H activation represent a distinct approach from the reported synthesis through C−Si bond formation by C( sp 3 )−H activation [18] . Due to the difference in bond formation positions, the approaches using silyldiazomethane are complementary and would provide a new synthetic strategy for silacycles.…”

Nickel/photoredox-catalyzed three-component silylacylation of acrylates via chlorine photoelimination

“…Among the various methods for C–Si bond formation, the silylfunctionalization of alkenes stands out as a particularly straightforward and atom-economic approach, converting common alkene feedstocks into valuable organosilicon derivatives. 2–9 The simultaneous introduction of a silicon unit and an additional functional group is invaluable for the rapid assembly of complex organosilicon frameworks. However, the development of efficient and practical methods for the 1,2-silyldifunctionalization of alkenes remains a significant challenge.…”

“…However, these methods face limitations due to the required preactivation of Si–M reagents 8 and their limited scope regarding silyl substituents. 2,9 This confines their utility primarily to simple silanes, reducing their effectiveness with bulkier silyl groups. On the other hand, radical-mediated silyl functionalization offers a viable alternative by directly activating hydrosilanes to form silyl radicals using external HAT regents, such as peroxides, or through oxidative pathways.…”

Unraveling the Role of Silyl and Silane in Si–Ni Catalysts for Hydrogenation

“…Organosilicon compounds are stable, nontoxic, and easy-handling, enabling them to be commonly employed in materials science, medicinal synthesis, and chemical transformation. , Unlike carbon, silicon has a large atomic radius and a low electronegativity, which usually acts as an electrophilic site or a protecting group (Scheme a). , The unique α/β silicon effect of organosilicon compounds makes them valuable reactants in hydrosilylation, cross-coupling, and other reactions. – Moreover, silicon plays a crucial role in forming Si–M bonds with metal centers and serving as a catalyst in various reactions. – …”