THE GYMNOCHROMES - NOVEL MARINE BROMINATED PHENANTHROPERYLENEQUINONE PIGMENTS FROM THE STALKED CRINOID GYMNOCRINUS-RICHERI
THE GYMNOCHROMES - NOVEL MARINE BROMINATED PHENANTHROPERYLENEQUINONE PIGMENTS FROM THE STALKED CRINOID GYMNOCRINUS-RICHERI
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DOI：
10.1021/jo00024a016
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发表时间：
1991-11-22
影响因子：
3.6
通讯作者：
DEBITUS, C
中科院分区：
文献类型：
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作者：
DERICCARDIS, F;IORIZZI, M;DEBITUS, C
从丽氏裸海百合（Gymnocrinus richeri）中分离得到5种新的溴代菲并吡喃醌类色素：裸色素A-D（1-4）和异裸色素D（5）。通过IR、UV-vis、H-1和C-13 NMR、FABMS等波谱数据推测了化合物的结构。在位置10和11处的大体积羟基和在位置3和4处的侧链两者的存在引起足够的拥挤，以迫使八环菲并萘醌系统成为非平面螺旋形状。这种螺旋性在分子中产生轴向手性。侧链中手性碳原子的存在产生非对映异构体。的手性碳和天然色素的轴向手性的绝对构型推断从CD和NMR数据和相关性与尾孢菌素和其他天然存在的perylenequinones。通过应用动力学拆分方法确定了化合物4和5侧链手性碳的构型。
Five novel brominated phenanthroperylenequinone pigments, gymnochromes A-D (1-4) and isogymnochrome D (5), were isolated from the stalked crinoid Gymnocrinus richeri. The structures of the compounds were inferred from their spectra (IR, UV-vis, H-1 and C-13 NMR, FABMS). The presence of both bulky hydroxy groups at positions 10 and 11 and side chains at positions 3 and 4 causes sufficient crowding to force the octacyclic phenanthroperylenequinone system into a nonplanar helical shape. This helicity generates axial chirality in the molecules. The presence of chiral carbon atoms in the side chains gives rise to diastereomers. The absolute configurations of the chiral carbons and the axial chirality of the natural pigments was inferred from CD and NMR data and by correlations made with cercosporin and other naturally occurring perylenequinones. The configurations assigned to the chiral carbons in the side chains of compounds 4 and 5 were confirmed by the results of the application of Horeau's method of kinetic resolution.