Synthesis and Properties of Planar-Chiral (η6-Benzene)(η5-cyclopentadienyl)ruthenium(II) Complexes in an Optically Pure Form
Synthesis and Properties of Planar-Chiral (η6-Benzene)(η5-cyclopentadienyl)ruthenium(II) Complexes in an Optically Pure Form
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光学纯形式平面手性(η6-苯)(η5-环戊二烯基)钌(II)配合物的合成与性能
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发表时间：
2001
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通讯作者：
Shigetoshi Takahashi
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作者：
Y. Matsushima;Nobuko Komatsuzaki;Yoshiki Ajioka;Mari Yamamoto;Hidetomo Kikuchi;Yasuyuki Takata;Noriko Dodo;K. Onitsuka;M. Uno;Shigetoshi Takahashi
合成了非对映体纯的平面手性环戊二烯基钌配合物[Ru（η5-1-CO 2 R *-2-Me-4-R1 C5 H2）（η6-C6 H6）][X]（4和8）（R* =（1）-或（d）-薄荷基; R1 = Me、Ph、t-Bu、2-萘基或4-BrC 6 H4; X = PF 6或BPh 4）。通过X射线晶体学分析确定了8b和4c（R_1 = Ph，t-Bu）的绝对构型，并根据它们的光学性质（包括圆二色光谱）对其他化合物的绝对构型进行了归属。对映体纯配合物（SC 1）-[Ru（η5-1-CONHBut-2-Me-4-R1 C5 H2）（η6-C6 H6）][PF 6] 9和-[Ru（η5-1-CONHBut-2-Me-4-R1 C5 H2）（η6-C6 H6）] [BPh 4] 10，以及（RC 1）-9和-10由非对映体配合物直接水解，然后与胺反应制得。9 e（R1 = 4-BrC 6 H4）中溴基的取代反应得到烷基、苯基和乙炔基衍生物。配合物[Ru（η5-1-CO2 Et-2-Me-4-R1 C5 H2）（η6-C6 H6）][PF 6] 6也转化为平面手性[Ru（η5-1-CO2 Et-2-Me-4-R1 C5 H2）（CH 3CN）3][X]，其经过配体交换反应得到了具有手性中心的碳环化合物[Ru（η5-1-CO2 Et-2-Me-4-R1 C5 H2）（CH 3CN）3][X]。
Planar-chiral cyclopentadienylruthenium complexes [Ru(η5-1-CO2R*-2-Me-4-R1C5H2)(η6-C6H6)][X] (4 and 8) (R* = (l)- or (d)-menthyl; R1 = Me, Ph, t-Bu, 2-Naphthyl, or 4-BrC6H4; X = PF6 or BPh4) were synthesized in a diastereomerically pure form. The absolute configuration of 8b and 4c (R1 = Ph, t-Bu) were determined by an X-ray crystallographic analysis and those of the others were assigned on the basis of their optical properties including their CD spectra. Enantiopure complexes (SC1)-[Ru(η5-1-CONHBut-2-Me-4-R1C5H2)(η6-C6H6)][PF6] 9 and -[Ru(η5-1-CONHBut-2-Me-4-R1C5H2)(η6-C6H6)] [BPh4] 10, and (RC1)-9 and -10 were prepared from direct hydrolysis of diastereomeric complexes, followed by the reaction of amines. Replacement reactions of the bromo group in 9e (R1 = 4-BrC6H4) gave alkyl, phenyl, and ethynyl derivatives. Complexes [Ru(η5-1-CO2Et-2-Me-4-R1C5H2)(η6-C6H6)][PF6] 6 were also transformed to planar-chiral [Ru(η5-1-CO2Et-2-Me-4-R1C5H2)(CH3CN)3][X], which underwent ligand exchange reactions to afford carb...