Alkyne insertion into cyclometallated pyrazole and imine complexes of iridium, rhodium and ruthenium; relevance to catalytic formation of carbo- and heterocycles
摘要:
环金属化配合物 [MCl(C⁁N)(环)](HC⁁N = 2-苯基吡唑,M = Ir,Rh 环 = Cp*;M = Ru,环 = 对伞花烃)很容易与 RCCR 进行插入反应( R = CO2Me, Ph) 得到单插入产物,铑配合物也与 PhCCH 区域特异性反应,得到类似的产物。环金属化亚胺配合物 [MCl(C^N)Cp*] (HC⁁N = PhCHNR, R = Ph, CH2CH2OMe, Me; M = Ir, Rh) 与 PhCCPh 的反应产物取决于取代基 R;当 R = CH2CH2OMe 时,观察到单插入,然而,对于 R = Me,初始插入产物不稳定,经历还原消除并损失有机片段,而对于 R = Ph,没有分离出含金属产物。与PhCCH一起,环金属化亚胺络合物可以得到单插入或双插入产物。讨论了串联 C-H 活化、炔插入机制催化合成碳环和杂环的影响。
Cycloruthenation of aryl imines and N-heteroaryl benzenes via C–H bond activation with Ru(II) and acetate partners
作者:Bin Li、Christophe Darcel、Thierry Roisnel、Pierre H. Dixneuf
DOI:10.1016/j.jorganchem.2015.02.050
日期:2015.9
N)(p-cymene) 3a-3d via ortho C–Hactivation/deprotonation by acetate. The presence of the stable Ru–Cl bond ratherthan a labile Ru–OAc bond is crucial for the isolation of the complexes. This preparative method of cyclometallates was applied to 2-phenyloxazoline, and benzo[h]quinoline and to the improved synthesis of 2-phenylpyridine and 1-phenylpyrazole derivatives. The molecularstructures of three cycloruthenates
芳烃与[RuCl 2(对-cymene)] 2和4当量的反应。的KOAc在甲醇引线到N-孺-C的形成室温下的cycloruthenates的RuCl(arylimine- ķ C,N)(p -cymene)3A-3D通过邻位C-H活化/去质子化由酯。稳定的Ru–Cl键而不是不稳定的Ru–OAc键的存在对于复合物的分离至关重要。这种环金属酸盐的制备方法应用于2-苯基恶唑啉和苯并[ h ]喹啉,以及用于改进的2-苯基吡啶和1-苯基吡唑衍生物的合成。报道了三种环钌酸酯的分子结构。