Silyloxyarenes as Versatile Coupling Substrates Enabled by Nickel-Catalyzed C–O Bond Cleavage
Silyloxyarenes as Versatile Coupling Substrates Enabled by Nickel-Catalyzed C–O Bond Cleavage
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DOI：
10.1021/acscatal.7b02025
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发表时间：
2017-07
期刊：
影响因子：
12.9
通讯作者：
Eric M. Wiensch;D. Todd;J. Montgomery
中科院分区：
文献类型：
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作者：
Eric M. Wiensch;D. Todd;J. Montgomery
硅烷氧基芳烃被证明是一种通用的基板类在各种镍催化偶联过程。使用Ti（O-i-Pr）4或三烷基硅烷作为试剂，使用具有N-杂环卡宾（NHC）配体的镍催化剂，芳基甲硅烷基醚的C（sp2）-O键直接转化为C-H或C-Si键。与甲硅烷基保护基团的有用特性相结合，这些方法使受保护的羟基能够直接参与高价值的键形成步骤，而不需要常规方法所需的脱保护-活化策略。甲硅烷基氧基芳烃的这些方法提供了与广泛使用的苯酚衍生物如新戊酸芳基酯、氨基甲酸酯和甲基醚互补的反应性，从而能够在没有保护基团和活化基团操作的情况下实现复杂底物的顺序化学选择性衍生化的有力策略。
Silyloxyarenes are demonstrated to be a versatile substrate class in a variety of nickel-catalyzed coupling processes. The C(sp2)–O bond of aryl silyl ethers is directly transformed into C–H or C–Si bonds using Ti(O-i-Pr)4 or trialkylsilanes as reagents using nickel catalysts with N-heterocyclic carbene (NHC) ligands. Paired with the useful characteristics of silyl protecting groups, these methods enable protected hydroxyls to directly participate in high-value bond-forming steps rather than requiring deprotection-activation strategies that conventional approaches require. These processes of silyloxyarenes provide reactivity complementary to widely used phenol derivatives such as aryl pivalates, carbamates, and methyl ethers, thus enabling a powerful strategy for sequential chemoselective derivatization of complex substrates without protecting group and activating group manipulations.