Facile Ar-CF3 bond formation at Pd.: Strikingly different outcomes of reductive elimination from [(Ph3P)2Pd(CF3)Ph] and [(Xantphos)Pd(CF3)Ph]
Facile Ar-CF3 bond formation at Pd.: Strikingly different outcomes of reductive elimination from [(Ph3P)2Pd(CF3)Ph] and [(Xantphos)Pd(CF3)Ph]
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DOI：
10.1021/ja064935c
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发表时间：
2006-10-04
影响因子：
15
通讯作者：
Marshall, William J.
中科院分区：
文献类型：
--
作者：
Grushin, Vladimir V.;Marshall, William J.
首次证明了金属中心（Pd）的简便且高选择性的全氟烷基芳基还原消除。在低至 50−80 °C 的温度下，[(Xantphos)Pd(Ph)CF3] 会发生非常干净的分解，以高产率和选择性产生 CF3Ph。相比之下，由刚性顺式螯合配体（例如 dppe）稳定的类似三氟甲基芳基钯在高达 130−140 °C 的温度下完全不反应。 [(Ph3P)2Pd(Ph)CF3] 在苯中、PhI 存在下于 60 °C 分解不会产生 PhCF3，而是以 2:1 的高选择性生成 [(Ph3P)2Pd(Ph)I] 和 [Ph4P]+[(Ph3P)Pd(CF3)3]-。
Facile and highly selective perfluoroalkyl−aryl reductive elimination from a metal center (Pd) has been demonstrated for the first time. At temperatures as low as 50−80 °C, [(Xantphos)Pd(Ph)CF3] undergoes remarkably clean decomposition to produce CF3Ph in high yield and selectivity. In contrast, analogous trifluoromethylpalladium aryls stabilized by rigid cis-chelating ligands such as dppe are completely unreactive at temperatures up to 130−140 °C. Decomposition of [(Ph3P)2Pd(Ph)CF3] in the presence of PhI in benzene at 60 °C does not produce PhCF3but rather leads to [(Ph3P)2Pd(Ph)I] and [Ph4P]+[(Ph3P)Pd(CF3)3]-in a 2:1 ratio with high selectivity.