Acetate Acetylacetonate Ampy Ruthenium(II) Complexes as Efficient Catalysts for Ketone Transfer Hydrogenation

Acetate Acetylacetonate Ampy Ruthenium(II) Complexes as Efficient Catalysts for Ketone Transfer Hydrogenation
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乙酸乙酰丙酮酸 Ampy 钌(II)配合物作为酮转移氢化的高效催化剂

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发表时间:
2020
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通讯作者:
W. Baratta
W. Baratta
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作者:
Daniela A. Hey;Michael J. Sauer;Paul J Fischer;Eva‐Maria H. J. Esslinger;F. E. Kühn;W. Baratta

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以乙酰丙酮为溶剂,通过质子化Ru(OAc)2(PPh 3)2,合成了乙酸乙酰丙酮钌(acac)膦配合物Ru(OAc)(acac)P2 [P2=(PPh 3)2,Ph 2 P(CH 2)4PPh 2(dppb)]. dppb衍生物与2-(氨甲基)吡啶(ampy)反应得到络合物Ru(OAc)(acac)(ampy)(dppb),其在甲苯中在90 °C下转化为[Ru(acac)(ampy)(dppb)](OAc)。在前一种衍生物中,ampy配体是单齿的,并通过NH 2-部分配位。所分离的acac络合物是酮转移氢化的活性催化剂,负载量低至0.01mol%,ampy具有很强的促进作用。 几种芳香族和脂肪族酮底物转化为它们相应的醇,并通过苯乙酮上的取代基的不同的电子影响是容忍的。
The mixed acetate acetylacetonate (acac) ruthenium(II) phosphine complexes Ru(OAc)(acac)P2 [P2=(PPh3)2, Ph2P(CH2)4PPh2 (dppb)] were prepared by protonation of Ru(OAc)2(PPh3)2 with acetylacetone in dichloromethane. Reaction of the dppb derivative with 2‐(aminomethyl)pyridine (ampy) affords the complex Ru(OAc)(acac)(ampy)(dppb), which converts to [Ru(acac)(ampy)(dppb)](OAc) in toluene at 90 °C. In the former derivative the ampy ligand is monodentate and coordinates through the NH2‐moiety. The isolated acac complexes are active catalysts for the transfer hydrogenation of ketones with loadings as low as 0.01 mol%, the ampy having a strong accelerating effect. Several aromatic and aliphatic ketone substrates are converted to their corresponding alcohols, and different electronic influences through substituents on acetophenone are tolerated.