Rhodium-Catalyzed Hydrolytic Cleavage of the Silicon–Carbon Bond of Silacyclobutanes to Access Silanols

Synthesis of Alkynylsilanes: A Review of the State of the Art

“…The ring opening or expansion reactions of silacycles provide an efficient strategy for enriching the structural and stereochemical diversity of silicon-containing compounds, ultimately contributing to the production of high-value products. [188][189][190][191] In 2021, the He group outlined the first protocol, utilizing silacyclobutanes (SCBs) as the silylating agents (Figure 50). [192] Key parameters included a 1:1.2 substrate ratio (SCB:silylacetylene), 2 mol% of [Rh-(cod)Cl] 2 , and 5 mol% of ligand by means of 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP).…”

“…Furthermore, silacycles have garnered significant attention as valuable precursors in diverse organic reactions. The ring opening or expansion reactions of silacycles provide an efficient strategy for enriching the structural and stereochemical diversity of silicon‐containing compounds, ultimately contributing to the production of high‐value products [188–191] …”

DFT study of rhodium-catalyzed transformation of silacyclobutane with alkyne or H2O: Si–Cl bond reductive elimination vs. alkyne insertion

“…More recently, Xu's group developed Rh/BINAP-catalyzed hydrolytic cleavage of the C–Si bond of SCB, achieving a clean synthesis of the silanol product 6 without side reactions (also known as O–H silylation, Scheme 1(c)). 15 Interestingly, both C(sp)–H silylation and O–H silylation were catalyzed by [Rh(cod)Cl] 2 /BINAP, yet two distinct reaction mechanisms were proposed, prompting further investigation into the underlying reasons.…”