首页> 外文期刊>Chemistry: A European journal >Multiple Condensation Reactions Involving Pt-II/Pd-II-OH2, Pt-NH3, and Cytosine-NH2 Groups: New Twists in Cisplatin-Nucleobase Chemistry
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Multiple Condensation Reactions Involving Pt-II/Pd-II-OH2, Pt-NH3, and Cytosine-NH2 Groups: New Twists in Cisplatin-Nucleobase Chemistry

机译:涉及Pt-II / Pd-II-OH2,Pt-NH3和胞嘧啶-NH2基团的多重缩合反应:顺铂-核碱基化学的新变化

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The coordination chemistry of the antitumor agent cisplatin and related complexes with DNA and its constituents, that is, the nucleobases, appears to be dominated by 1:1 and 1:2 adducts of the types cis-[Pta(2)(nucleobase)X] and cis-[Pta(2)(nucleobase)(2)] (a=NH3 or amine; a(2)=diamine or diimine; X=Cl, OH or OH2). Here, we have studied the interactions of the putative 1:1 adducts cis-[Pta(2)(1-MeC-N3)(OH2)](2+) (with a=NH3, a(2)=2,2-bpy (2,2-bipyridine), 1-MeC=model nucleobase 1-methylcytosine) with additional cis-[Pt(NH3)(2)(OH2)(2)](2+) or its kinetically superior analogues [Pd(en)(OH2)(2)](2+) (en=ethylenediamine) and [Pd(2,2-bpy)(OH2)(2)](2+). Depending upon the conditions applied different compounds of different nuclearity are formed. Without exception they represent condensation products of the components, containing -1-MeC-H, -OH-, as well as -NH2- bridges. In the presence of Ag+ ions, the isolated products in several cases display additionally PtAg dative bonds. On the basis of the cytosine-containing structures established by X-ray crystallography, it is proposed that any of the feasible initial 1:1 nucleobase adducts of cisplatin could form dinuclear Pt complexes upon reaction with additional hydrolyzed cisplatin, thereby generating nucleobase adducts other than the presently established ones. Two findings appear to be of particular significance: First, hydrolyzed cisplatin can have a moderately accelerating effect on the formation of a secondary nucleobase product. Second, NH3 ligands of the cisplatin moiety can be converted into bridging amido ligands following condensation with the diaqua species of cisplatin.
机译:抗肿瘤药顺铂及其相关复合物与DNA及其成分(即核碱基)的配位化学似乎由顺式[Pta(2)(nucleobase)X类型的1:1和1:2加合物控制]和顺式[Pta(2)(核碱基)(2)](a = NH3或胺; a(2)=二胺或二亚胺; X = Cl,OH或OH2)。在这里,我们研究了推定的1:1加合物顺式[[Pta(2)(1-MeC-N3)(OH2)](2+)(其中a = NH3,a(2)= 2,2)的相互作用-bpy(2,2-bipyridine),1-MeC =模型核碱基1-甲基胞嘧啶)带有额外的cis- [Pt(NH3)(2)(OH2)(2)](2+)或其动力学上优越的类似物[Pd (en)(OH2)(2)](2+)(en =乙二胺)和[Pd(2,2-bpy)(OH2)(2)](2+)。根据所应用的条件,形成具有不同核的不同化合物。它们毫无例外地代表包含-1-MeC-H,-OH-和-NH2-桥的组分的缩合产物。在存在Ag +离子的情况下,在某些情况下,分离出的产物还显示出PtAg固有键。根据X射线晶体学确定的含胞嘧啶的结构,建议顺铂的任何可行的初始1:1核碱基加合物在与其他水解顺铂反应后都可以形成双核Pt络合物,从而生成除目前建立的。有两个发现似乎具有特别重要的意义:首先,水解的顺铂可对次级核碱基产物的形成产生中等程度的促进作用。第二,在与顺铂的diaqua物种缩合后,顺铂部分的NH 3配体可以转化为桥联酰胺配体。

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