Substituted Functional Olefins Through Lateral Sequential Lithiation/Silylation/Condensation of Tertiary Aromatic Amides: A Ligand for Phosphane‐Free Palladium‐Catalyzed Suzuki Coupling Reactions
Substituted Functional Olefins Through Lateral Sequential Lithiation/Silylation/Condensation of Tertiary Aromatic Amides: A Ligand for Phosphane‐Free Palladium‐Catalyzed Suzuki Coupling Reactions
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DOI：
10.1002/ejoc.201101284
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发表时间：
2012
影响因子：
2.8
通讯作者：
Li‐Wen Xu;Xihui Chen;Hao Shen;Yuan Deng;Jianxiong Jiang;K. Jiang;G. Lai;Chun-qi Sheng
中科院分区：
文献类型：
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作者：
Li‐Wen Xu;Xihui Chen;Hao Shen;Yuan Deng;Jianxiong Jiang;K. Jiang;G. Lai;Chun-qi Sheng
已经开发了叔芳族酰胺的前所未有的侧向顺序锂化/甲硅烷基化/缩合，其提供了以良好产率建立官能烯烃的有效方法。此外，我们还建立了一个简单有效的方法，包括UV/维斯，荧光和NMR分析，以检测过渡金属盐和功能性烯烃之间的相互作用含有叔酰胺。这使得能够开发在叔芳酰胺衍生的烯烃配体存在下的高效钯催化的铃木偶联反应。通过使用2 mol-% Pd（0Ac）2、2当量Pd（0Ac）2、2当量Pd（0Ac）3和2当量Pd（0Ac）4获得最佳结果。Cs2 CO 3，反应温度80 ℃，二氧六环作为溶剂，无膦烯烃2d作为配体。
An unprecedented lateral sequential lithiation/silylation/condensation of tertiary aromatic amides has been developed that provides an efficient method to build up functional olefins in good yields. In addition, we have established an efficient and simple method that involves UV/Vis, fluorescence, and NMR analyses, to detect the interaction between transition-metal salts and functional olefins containing tertiary amides. This has enabled a highly efficient palladium-catalyzed Suzuki coupling reaction in the presence of tertiary aromatic amide-derived olefin ligands to be developed. The best results were obtained by employing 2 mol-% Pd(OAc)2, 2 equiv. Cs2CO3, a reaction temperature of 80 °C, dioxane as the solvent, and phosphane-free olefin 2d as ligand.