Deoxygenative Silylation of C(sp<sup>3</sup>)?O Bonds with Hydrosilane by Cooperative Catalysis of Gold Nanoparticles and Solid Acids
Deoxygenative Silylation of C(sp<sup>3</sup>)?O Bonds with Hydrosilane by Cooperative Catalysis of Gold Nanoparticles and Solid Acids
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金纳米粒子与固体酸协同催化C(sp<sup>3</sup>)?O键与氢硅烷的脱氧硅烷化反应
DOI：
10.1021/acscatal.3c00973
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发表时间：
2023
期刊：
影响因子：
12.9
通讯作者：
Shishido Tetsuya
中科院分区：
文献类型：
--
作者：
Miura Hiroki;Yasui Yuki;Masaki Yosuke;Doi Masafumi;Shishido Tetsuya
描述了负载型Au催化剂用于C（sp 3）-O键与氢硅烷的高效脱氧硅烷化反应。负载在TiO 2上的金纳米颗粒使各种氢硅烷能够在C-Si交叉偶联反应中用作硅基的来源。各种烷基乙酸酯和炔丙基碳酸酯参与Au催化的反应，以高产率提供相应的烷基和丙二烯基硅烷。此外，Au/TiO 2对环醚的开环硅烷化反应也是有效的。详细的机理研究证实，该反应涉及到硅基和烷基自由基中间体的形成，而作为单电子转移催化剂的Au纳米颗粒和金属氧化物表面的刘易斯酸中心的协同作用是导致氢硅烷对特定C（sp3）-Si键形成的异常反应性的原因.
Efficient deoxygenative silylation of C(sp3)–O bonds with hydrosilanes by supported Au catalysts is described. Gold nanoparticles supported on TiO2enabled various hydrosilanes to be used as sources of silyl groups in C–Si cross-coupling reactions. A variety of alkyl acetates and propargyl carbonates participated in the Au-catalyzed reactions to furnish the corresponding alkyl and allenylsilanes in high yields. In addition, Au/TiO2was also effective for ring-opening silylation of cyclic ethers. A detailed mechanistic investigation corroborated that the title reaction involves the formation of silyl and alkyl radical intermediates, and the cooperation of Au nanoparticles as single-electron transfer catalysts and Lewis acid sites at the surface of metal oxides was responsible for the unusual reactivity of hydrosilanes for specific C(sp3)–Si bond formation.