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 c...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.展开更多
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...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.展开更多
The Alkoxylsilanes were synthesized by means of solvent method to methanolyze methyl-substituted chlorosilanes .The methanolysis was investigated under different reaction conditions:temperature,various solvents and dr...The Alkoxylsilanes were synthesized by means of solvent method to methanolyze methyl-substituted chlorosilanes .The methanolysis was investigated under different reaction conditions:temperature,various solvents and dropping manner.Thas provide available experimental data for synthesizing these kinds of organo-silicone monomers.展开更多
基金financial support from the National Natural Science Foundation of China(21901206)Postdoctoral Science Foundation of China(2022M712589)+2 种基金General key R&D Projects in Shaanxi Province(2023-YBGY-321)Natural Science Foundation of Chongqing(CSTB2022NSCQ-MSX0826)Fundamental Research Funds for the Central Universities and the Haihe Laboratory of Sustainable Chemical Transformation.
文摘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.
基金the National Natural Science Foundation of China for its financial support(No.22071084).
文摘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.
文摘The Alkoxylsilanes were synthesized by means of solvent method to methanolyze methyl-substituted chlorosilanes .The methanolysis was investigated under different reaction conditions:temperature,various solvents and dropping manner.Thas provide available experimental data for synthesizing these kinds of organo-silicone monomers.
