Double Deprotonation of Pyridinols Generates Potent Organic Electron-Donor Initiators for Haloarene-Arene Coupling
Double Deprotonation of Pyridinols Generates Potent Organic Electron-Donor Initiators for Haloarene-Arene Coupling
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DOI：
10.1002/anie.201511847
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发表时间：
2016-03-24
影响因子：
16.6
通讯作者：
Murphy, John A.
中科院分区：
文献类型：
--
作者：
Barham, Joshua P.;Coulthard, Graeme;Murphy, John A.
卤代芳烃与芳烃的无过渡金属偶联，在有机添加剂存在下通过使用碱金属醇盐引发，在文献中受到显著关注。大多数已知的有机添加剂实现碘代芳烃与芳烃的偶联，而不是溴代芳烃。最近报道2-吡啶甲醇（11）将反应扩展到芳基溴。本文探讨了反应机理，并报道了11衍生的二价阴离子作为电子给体引发反应的证据。它还提出了贫电子苯甲酰基衍生物可以转化为电子供体，以引发这些反应的路线。
Transition metal-free couplings of haloarenes with arenes, triggered by the use of alkali metal alkoxides in the presence of an organic additive, are receiving significant attention in the literature. Most of the known organic additives effect coupling of iodoarenes, but not bromoarenes, to arenes. Recently it was reported that 2-pyridinecarbinol (11) extends the reaction to aryl bromides. This paper investigates the mechanism, and reports evidence for dianions derived from 11 as electron donors to initiate the reaction. It also proposes routes by which electron-poor benzoyl derivatives can be transformed into electron donors to initiate these reactions.