Iron-Catalyzed Reductive C(aryl)—Si Cross-Coupling of Diaryl Ethers with Chlorosilanes

The reductive cross-coupling between C(aryl)—O and Si—Cl bonds is of much importance as a valuable strategy for the construction of C(aryl)—Si bonds but has remained a great challenge.Herein,we report a reductive cross-coupling of diaryl ethers and chlorosilanes via strong electrophilic C(aryl)—O and Si—Cl bonds cleavage by iron catalysis,which constitutes an efficient protocol for the synthesis of a range of functionalized arylsilanes.The combination of low cost FeCl2 as the precatalyst and iPrMgCl as the reductant shows high activity in the successive cleavage of unactivated C(aryl)—O bonds of diaryl ethers and strong electrophilic Si—Cl bonds of chlorosilanes,allowing their cross-coupling in a reductive fashion.The low-valent iron species generated in situ by reduction of FeCl2 with iPrMgCl was proposed,which prefers to initially cleavage the C(aryl)—O bond of diaryl ethers with the chelation help of an o-amide auxiliary.

Surface Modification of Montmorillonites by Chlorosilanes

Montmorillonite was modified by chlorosilane derivatives (trimethylchlorosilane and tert butyldimethylchlorosilane) bas^ed on the reaction between OH group and chlorosilane. Fourier transformed infrared spectra (FTIR) confirmed that chlorosilanes did react with the OH groups of montmorillonite. The effect of reaction time and dispersing agents on the intercalation was studied by wide angle X ray diffraction (WAXD) method. Further experiments proved that there is no reactive OH group on the surface of layers in the interlayer galleries of montmorillonite. The cation exchange capacity (CEC) of montmorillonites was measured, showing that after modification by chlorosilane derivatives, CEC values drastically decreased. The dispersibility measurements of montmorillonites were conducted, which showed that the dispersibility of modified montmorillonites both in H 2O and toluene were improved due to the decrease of attractions of particles and layers.

Mn-mediated reductive C(sp3)–Si coupling of activated secondary alkyl bromides with chlorosilanes

The construction of secondary alkylsilanes is a challenging subject in the synthetic community.The cross-coupling provides a practical solution to address this problem,but it typically relies on organometallic species.Herein,we report an Mn-mediated reductive C(sp^(3))-Si coupling to synthesize these compounds from alkyl and silyl electrophiles.This approach avoids the requirement for activation of Si-Cl by transition metals and thus allows for the coupling of various common chlorosilanes.The reaction proceeds under mild conditions and shows good functional group compatibility.The method offers access toα-silylated organophosphorus and sulfones with a scope that is complementary to those obtained from the established methods.