Pteridine. Teil XCIV. Synthese und Eigenschaften von 5,6‐Dihydro‐6‐(1,2,3‐trihydroxypropyl)pteridinen: Kovalente intramolekulare Addukte
Pteridine. Teil XCIV. Synthese und Eigenschaften von 5,6‐Dihydro‐6‐(1,2,3‐trihydroxypropyl)pteridinen: Kovalente intramolekulare Addukte
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蝶啶 XCIV。
DOI：
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发表时间：
1990
期刊：
影响因子：
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通讯作者：
R. Prewo
中科院分区：
文献类型：
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作者：
Rainer Soyka;W. Pfleiderer;R. Prewo
蝶呤类化合物：5，6-Dihydro-6-(1，2，3-trihydroxypropyl)pteridines：共价分子内加合物的合成与性质
不同的5，6-二氨基嘧啶(1，15，24，33)与L-(2)和D-阿拉伯糖(3)的苯肼在N_2的酸性介质中缩合得到形式的5，6-dihydro-6-(1，2，3-trihydroxypropyl)pteridines(见4和5)，后者优先以分子内加合物的形式存在，六氢吡喃-[3，2-g]蝶啶6，7，16，17，25，26和34，随后通过将侧链的末端羟基加成到蝶啶部分的C(7)N(8)键上而形成。光谱分析还检测到六氢呋喃并[3，2-g]蝶啶10、11、18、19和35是平衡混合物中的次要成分。在4-氨基-2-(甲硫基)蝶啶系列中，6和7的结晶分别得到了立体化学纯的(3S，4R，4AR，10aS)-6-amino-3，4，4a，5，10，10a-hexahydro-8-(methylthio)-2H-pyrano[3，2-g]pteridine-3，4-diol(8))及其对应的对映体9，结构8经X-射线分析证实。六氢吡喃并[3，2-g]蝶啶的酰化反应得到了更稳定的三乙酰、四乙酰和五乙酰衍生物12-14、20-23、27-32和37-39，对它们进行了表征，并确定了它们的绝对和相对构型(1H-和13C-核磁共振和紫外光谱，手性测量，元素分析)。
Pteridines: Synthesis and Characteristics of 5,6-Dihydro-6-(1,2,3-trihydroxypropyl)pteridines: Covalent Intramolecular Adducts
Various 5,6-diaminopyrimidines (1, 15, 24, 33) were condensed with the phenylhydrazones of L-(2) and D-arabinose (3) in acidic medium under N2 to give formal 5,6-dihydro-6-(1,2,3-trihydroxypropyl)pteridines (see, e.g., 4 and 5), the latter turned out to exist preferentially as intramolecular adducts, the hexahydropyrano-[3,2-g]pteridines 6, 7, 16, 17, 25, 26, and 34, formed subsequently by addition of the terminal OH group of the side-chain to the C(7)N(8) bond of the pteridine moiety. Spectroscopically, the isomeric hexahydrofuro-[3,2-g]pteridines 10,11,18,19, and 35 were also detected as minor components in the equilibrium mixtures. In the 4-amino-2-(methylthio)pteridine series, crystallization of 6 and 7 led to the stereochemically pure (3S,4R,4aR, 10aS)-6-amino-3,4,4a,5,10,10a-hexahydro-8-(methylthio)-2H-pyrano[3,2-g]pteridine-3,4-diol (8) and its corresponding enantiomer 9, respectively Structure 8 was proven by X-ray analysis. Acylation of the hexahydropyrano[3,2-g]pteridines yielded the more stable tri-, tetra-, and pentaacetyl derivatives 12–14, 20–23, 27–32, and 37–39 which were characterized and of which the absolute and relative configurations were determined (1H- and 13C–NMR and UV spectra, chiroptical measurements, elemental analyses).