A new set of nickelacyclic carboxylates (“nickelalactones”) containing pyridine as supporting ligand: synthesis, structures and application in C–C– and C–S– linkage reactions
作者:Jens Langer、Reinald Fischer、Helmar Görls、Dirk Walther
DOI:10.1016/j.jorganchem.2004.04.047
日期:2004.9
(Me2(2-py)2Si) under exchange of the pyridine ligands to give 1c. 1a–3a and their bipy derivatives react with di-p-tolyldisulfide to form β-thioesters upon workup. Furthermore, reaction of 2-bromopropiophenone with nickelacycles of the type 2 results in the formation of 3,4-diethyl-6-hydroxy-5-methyl-6-phenyl-5,6-dihydro-2H-pyrane-2-one in good yields (64–75%). These reactions offer attractive new preparative
[(py)2 Ni(CH 2 CH 2 COO)](1a),[(py)2 Ni(C(Et)C(Et)–COO)](2a)和[(py)合成了Ni(CH 2 C(CH 3)C(CH 3)–CH 2 -COO)](3a),并通过NMR,IR光谱以及在1a和2a情况下的X射线衍射分析对其结构进行了研究。在图1A和2A的镍(II)离子具有正方形平面的几何形状,在对比的是η 3烯丙基化合物[(联吡啶)镍(CH 2 C(CH 3)C(CH3)–CH 2 –COO)](3b),其中镍中心采用方形金字塔形几何形状。1a在吡啶配体交换下与二(2-吡啶基)二甲基硅烷(Me 2(2-py)2 Si)反应,得到1c。1a – 3a及其联吡啶衍生物在后处理过程中与二对甲苯基二硫化物反应形成β-硫酯。此外,与该类型的nickelacycles 2-溴苯丙酮的反应2在3,4-二乙基-6-羟基-5-甲基-6-苯基-5,6-