TOTAL SYNTHESIS AND ABSOLUTE STEREOCHEMISTRY OF (+)-XESTOQUINONE AND XESTOQUINOL
TOTAL SYNTHESIS AND ABSOLUTE STEREOCHEMISTRY OF (+)-XESTOQUINONE AND XESTOQUINOL
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DOI：
10.1021/jo00297a035
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发表时间：
1990-05-11
影响因子：
3.6
通讯作者：
KURIKI, T
中科院分区：
文献类型：
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作者：
HARADA, N;SUGIOKA, T;KURIKI, T
从热带海洋海绵中分离得到了具有生物活性的海洋天然产物(+)-xestoquinone 1。光纯羟甲基酮衍生物(4aR,5S,8aR)-(+)-8经8步反应转化为烯酮(+)-15。（+）-15与3,6-二甲氧基苯并环丁烯（16）的Diels-Alder反应生成了四环体系的加合物(+)-17，经一系列五步反应转化为(12bS)-xestoquinone 1。合成样品的CD谱与天然xestoquinone(+)-1的CD谱一致。因此，确定(+)-xestoquinone 1的绝对立体化学为12bS。最后，xestoquinone (12bS)-(+)-1被转化为xestoquinol (12bS)-2，尽管xestoquinol 2本身尚未作为天然产物被分离出来。通过萘-二烯衍生物22的CD谱与模型化合物(12bS)-23的理论计算CD曲线的比较，确定了xestoquinone 1的绝对构型。
The first total synthesis of (+)-xestoquinone 1, a biologically active marine natural product isolated from tropical marine sponges, was achieved. Optically pure hydroxymethyl ketone derivative (4aR,5S,8aR)-(+)-8 was converted to enone (+)-15 via the reactions of eight steps. The Diels-Alder reaction of (+)-15 with 3,6-dimethyoxybenzocyclobutene (16) afforded an adduct (+)-17 of a tetracyclic system, which was converted to (12bS)-xestoquinone 1 via a series of five-step reactions. The CD spectrum of the synthetic sample was identical with that of the natural xestoquinone (+)-1. Therefore, the absolute stereochemistry of (+)-xestoquinone 1 was determined to be 12bS. Finally, xestoquinone (12bS)-(+)-1 was converted to xestoquinol (12bS)-2, although xestoquinol 2 itself has not been isoalted yet as a natural product. The absolute configuration of xestoquinone 1 was also established by the comparison of the CD spectrum of naphthalene-diene derivative 22 with the theoretically calculated CD curve of a model compound (12bS)-23.