Rare-Earth-Catalyzed Selective 1,4-Hydrosilylation of Branched 1,3-Enynes Giving Tetrasubstituted Silylallenes
Rare-Earth-Catalyzed Selective 1,4-Hydrosilylation of Branched 1,3-Enynes Giving Tetrasubstituted Silylallenes
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稀土催化支链 1,3-烯炔的选择性 1,4-氢化硅烷化得到四取代的硅联烯
DOI：
10.1021/jacs.1c04689
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发表时间：
2021-08-13
影响因子：
15
通讯作者：
Cui, Chunming
中科院分区：
文献类型：
--
作者：
Chen, Wufeng;Jiang, Chunhui;Cui, Chunming
丙二烯因其反应活性的多样性，在有机合成和药物化学中有着广泛的应用。催化1，3-烯炔的1，4-硅氢加成反应是合成硅烷基联烯的直接途径。然而，过渡金属催化的反应一直没有成功，由于选择性差，底物范围非常有限。我们在这里报告的有效和选择性的1，3-烯炔的支化的1，4-硅氢加成启用的烯-二氨基稀土酸盐催化剂使用烷基和芳基氢化硅烷，导致排他性的四取代的硅烷基联烯的形成。通过氘代反应、动力学研究和密度泛函理论（DFT）计算对反应机理进行了探讨，揭示了稀土催化剂的高刘易斯酸性、大离子半径和酸盐结构在反应中的重要作用.
Allenes are versatile synthons in organic synthesis and medicinal chemistry because of their diverse reactivities. Catalytic 1,4-hydrosilylation of 1,3-enynes may present the straightforward strategy for synthesis of silylallenes. However, the transition-metal-catalyzed reaction has not been successful due to poor selectivity and very limited substrate scopes. We report here the efficient and selective 1,4-hydrosilylation of branched 1,3-enynes enabled by the ene-diamido rare-earth ate catalysts using both alkyl and aryl hydrosilanes, leading to the exclusive formation of tetrasubstituted silylallenes. Deuteration reaction, kinetic study, and DFT calculations were conducted to investigate the possible mechanism, revealing crucial roles of high Lewis acidity, large ionic radius, and ate structure of the rare-earth catalysts.