作者:Natalie M. Scott、Thomas Schareina、Oleg Tok、Rhett Kempe
DOI:10.1002/ejic.200400228
日期:2004.8
aminopyridinate). Deprotonation of Ap*H in diethyl ether using BuLi results (after workup in hexane) in a colourless crystalline material. X-ray structural analysis reveals it to be a monomeric three-coordinate lithium aminopyridinate. In toluene solution, an equilibrium between [(Ap*Li)2] (in excess at room temperature) and [Ap*Li(OEt2)] (prominent at low temperature) is observed. Reaction of Ap′H with BuLi in diethyl
原位形成的 1-溴-2,4,6-二异丙苯 (1) 或 1-溴-2,6-二甲基苯 (2) 的格氏化合物与 2,6-二溴吡啶在催化作用下的反应[(dme)NiBr2](dme = 1,2-二甲氧基乙烷)和三环己基膦(1:2 比例)的量产生相应的单芳基化溴吡啶。这些溴吡啶与 2,6-二异丙基苯胺进行 Pd 催化的芳基胺化(Buchwald-Hartwig 胺化),生成(2,6-二异丙基苯基)[6-(2,4,6-三异丙基苯基)吡啶-2-基]胺( Ap*H)和(2,6-二异丙基苯基)[6-(2,6-二甲基苯基)吡啶-2-基]胺(Ap'H)(Ap=氨基吡啶酸盐)。使用 BuLi 在乙醚中对 Ap*H 进行去质子化,结果(在己烷中处理后)为无色结晶材料。X 射线结构分析表明它是一种单体三配位氨基吡啶酸锂。在甲苯溶液中,观察到 [(Ap*Li)2](室温下过量)和 [Ap*Li(OEt2)](低温下突出)之间的平衡。Ap'H