Dinuclear ruthenium(I) complexes of the type [Ru2(CO)4L2] with carboxylate or 2-pyridonate ligands: Evaluation as catalysts for olefin cyclopropanation with diazoacetates
作者:Thorsten Werle、Lutz Schäffler、Gerhard Maas
DOI:10.1016/j.jorganchem.2005.06.043
日期:2005.12
Dinuclear ruthenium(I,I) carboxylate complexes [Ru2(CO)4(μ-OOCR)2]n (R = CH3 (1a), C3H7 (1b), H (1c), CF3 (1d)) and 2-pyridonate complex [Ru2(CO)4(μ-2-pyridonate)2]n (3) catalyze efficiently the cyclopropanation of alkenes with methyl diazoacetate. High yields are obtained with terminal nucleophilic alkenes (styrene, ethyl vinyl ether, α-methylstyrene), medium yields with 1-hexene, cyclohexene, 4,5-dihydrofuran
双核钌(I,I)羧酸盐配合物[Ru 2(CO)4(μ-OOCR)2 ] n(R = CH 3(1a),C 3 H 7(1b),H(1c),CF 3(1d))和2-丙酮酸酯络合物[Ru 2(CO)4(μ-2-吡啶酮酸酯)2 ] n(3)有效地催化重氮乙酸甲酯对烯烃的环丙烷化。用末端亲核烯烃(苯乙烯,乙基乙烯基醚,α-甲基苯乙烯)可获得高产率,用1-己烯,环己烯,4,5-二氢呋喃和2-甲基-2-丁烯可获得中等产率。由单取代的烯烃和环烯烃获得的环丙烷的E-选择性以1b > 1a > 1d > 1c的顺序降低。2-甲基-2-丁烯的环丙烷化是高度顺选择性的。的类型的几个络合物的[Ru 2(CO)4(μ-L 1)2 ] 2(第四)和(5),的[Ru 2(CO)4(μ-L 1)2大号2 ](L 2 = CH 3 OH,PPH 3)(6) - (9)和的[Ru 2(CO)4( CH 3 CN)2(μ-L