Recent Progress in the Transition‐Metal‐Catalyzed Activation of Si−Si Bonds To Form C−Si Bonds

Abstract

Disilanes possessing a Si-Si bond are unique element-element species. Transition-metal-catalyzed activation of the Si-Si bond allows many useful transformations that generate diverse organosilanes. This Minireview highlights impressive developments in this field over the past decade, with an emphasis on the formation of vinyl-, aryl-, and acylsilanes by C(sp )-Si bond formation as well as the formation of allyl- and alkylsilanes by C(sp )-Si bond formation.

Electrochemical logic to synthesize disilanes and oligosilanes from chlorosilanes

“…Linear and cyclic oligosilanes have attracted considerable interest in organic synthesis and material science 1,2,3 . Disilanes are versatile reagents for the construction of C-Si bonds via transition-metal catalyzed Si-Si bond activation, which provide convenient access to a range of organosilane building blocks (Figure 1a) 2,3,4 . Disilanes are also attractive alternatives to hydrosilane reagents in silylation reactions, owing to their greater stability, ease of handling, and because their second silyl group can sequester the leaving group (e.g., by forming strong Si-O or Si-X bonds) thereby creating a strong…”

Nickel-Mediated Enantiospecific Silylation via Benzylic C–OMe Bond Cleavage

“…Despite the success of Grignard reagents (unhindered) as a coupling partner in C­(sp 3 )–OMe bond cleavage, the cross-coupling reactions of ethers remain essentially limited to C–C bond-forming reactions. On the contrary, organosilicons (C–Si bond) have widespread applications across various disciplines − and are versatile intermediates in organic synthesis. − Consequently, considerable effort in cross-coupling reactions has been spent to contribute to the synthesis of organosilanes, including silylation via C–N bond cleavage (Scheme b). − Recently, for the first time, we introduced an economical Me 3 SiMgI (directly synthesized from TMSI) in cross-coupling reactions [C­(sp 2 )–OCb bond cleavage] for the synthesis of ArSiMe 3 , a useful organosilane for further synthetic transformations (Scheme b).…”

(3 + 2)-Annulation of 1,3-N,Si-tetraorganosilane reagents TsHNCH2SiBnR1R2 with arynes for efficient synthesis of 3-silaindolines

“…On the other hand, it should also possess enough reactivity for the formation of a new Si–C bond, leading to annulation. In this regard, tetraorganosilanes bearing four Si–C bonds emerge as one of the potential candidates, because they are stabler and easier to handle than silyl chlorides (Si–X), 11 hydrosilanes (Si–H), 12 borosilanes (Si–B) 13 or disilanes (Si–Si), 14 typically used for Si–C bond formation. However, application of tetraorganosilanes to forming a new Si–C bond remains challenging, primarily due to the low dissociation activity of their Si–C bonds making them typically inert.…”