Alkali-Metal-Catalyzed Cross-Dehydrogenative Couplings of Hydrosilanes with Amines
Alkali-Metal-Catalyzed Cross-Dehydrogenative Couplings of Hydrosilanes with Amines
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DOI：
10.1002/cctc.201501356
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发表时间：
2016-04-06
期刊：
影响因子：
4.5
通讯作者：
Panda, Tarun K.
中科院分区：
文献类型：
--
作者：
Anga, Srinivas;Sarazin, Yann;Panda, Tarun K.
报道了在温和条件下，以1族金属六甲基二硅氮化物[MN(SiMe3)(2)](M=Li，Na，K)为前催化剂，氢硅烷和胺的N-H/H-Si交叉脱氢偶联反应(CDC)，反应转化率和化学选择性都很高。[KN(SiMe3)(2)]表现出比同属锂盐和钠盐更高的活性。催化的CDC反应具有广阔的底物范围。苯基硅烷和二苯基硅烷在环境条件下与许多胺反应；三苯基硅烷需要更高的温度才能进行CDC反应。分离并表征了中间体锂配合物[(THF)(2)Li-{N(SiHPh2)(Dipp)}](1)。
We report the N-H/H-Si cross-dehydrogenative coupling (CDC) of hydrosilanes and amines with high conversion (>90%) and chemoselectivity for the production of silazanes, using group1 metal hexamethyldisilazides [MN(SiMe3)(2)] (M=Li, Na, K) as precatalysts under mild conditions. [KN(SiMe3)(2)] showed higher activity than the congeneric lithium and sodium salts. The catalyzed CDC reaction displays a broad substrate scope. Phenylsilane and diphenylsilane react with a number of amines under ambient conditions; more elevated temperature is required for triphenylsilane to undergo CDC reactions. The intermediate lithium complex [(THF)(2)Li-{N(SiHPh2)(Dipp)}] (1) has been isolated and characterized in an attempt to identify the operative reaction mechanism.