Biaryls made easy: PEPPSI and the Kumada-Tamao-Corriu reaction
Biaryls made easy: PEPPSI and the Kumada-Tamao-Corriu reaction
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DOI：
10.1002/chem.200601360
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发表时间：
2007-01-01
影响因子：
4.3
通讯作者：
Valente, Cory
中科院分区：
文献类型：
--
作者：
Organ, Michael G.;Abdel-Hadi, Mirvat;Valente, Cory
详细描述了一种易于使用的、高度通用的Kumada-Tamao-Corriu（KTC）方案，其利用PEPPSI（吡啶、增强、预催化剂、制备、稳定和引发）预催化剂1和2。这些催化剂的易用性以及以高产率合成各种受阻联芳基化合物、大的偶联配偶体和药物样杂环化合物使得PEPPSI-KTC方案非常有吸引力。PEPPSI系统的高反应性允许首次使用任何方案在室温下合成四邻位取代的杂环11。PEPPSI方案也容许Boc保护基，并且酚在改性条件下不需要保护。还进行了相对大规模（10 g）的反应，而没有性能损失。此外，将PEPPSI-IPr，1与先前报道的高活性膦配体42、43和44进行比较，并且显示在相同条件下产生显著更好的产率。最后，我们证明了PEPPSI催化剂系统非常擅长进行顺序KTC偶联反应，类似于多组分反应，其允许在一个单一操作中产生复杂的聚芳基和聚杂芳基结构。
An easily employed, highly versatile Kumada-Tamao-Corriu (KTC) protocol utilizing the PEPPSI (Pyridine, Enhanced, Precatalyst, Preparation, Stabilization and Initiation) precatalysts 1 and 2 is detailed. The ease-of-use of these catalysts and the synthesis of a wide range of hindered biaryls, large coupling partners and drug-like heterocycles, in high yield, makes the PEPPSI-KTC protocol very attractive. The high reactivity of the PEPPSI system allowed a tetra-ortho-substituted heterocycle, 11 to be synthesized at room temperature for the first time using any protocol. The PEPPSI protocols also tolerated the Boc protecting group and phenols required no protection in modified conditions. A relatively large scale (10 g) reaction was also performed with no loss in performance. Furthermore, PEPPSI-IPr, 1, was compared to previously reported highly active phosphine ligands 42, 43, and 44 and was shown to result in significantly better yields under identical conditions. Finally, we demonstrated that the PEPPSI catalyst system is very adept at performing sequential KTC coupling reactions, analogous to multicomponent reactions, which allow complex polyaryl and polyheteroaryl architectures to be produced in one single operation.