Chemistry of anti- and syn-1,2:3,4-naphthalene dioxides and their potential relevance as metabolic intermediates
Chemistry of anti- and syn-1,2:3,4-naphthalene dioxides and their potential relevance as metabolic intermediates
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反-和顺-1,2:3,4-二氧化萘的化学及其作为代谢中间体的潜在相关性
DOI：
10.1021/jo00148a021
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发表时间：
1982
影响因子：
3.6
通讯作者：
W. Stillwell
中科院分区：
文献类型：
--
作者：
W. Tsang;G. Griffin;M. Horning;W. Stillwell
进一步证实了甲氧基离子对La的苄基氯和C-4位的进攻占优势，给出了4a。从二元醇4a制备了二甲基磺酸酯4b，并保留了后者的相关核磁共振光谱特征。用高铁丁醇钾处理后，4b转化为与1，4-二甲氧基萘(9)的真实样品在所有方面都相同的二甲醚。值得注意的是，与La相反，氧化萘2在2-位上经历了甲基氧离子和其他亲核试剂的开环。5这可能归因于在C-2位增加了烯丙基性质，这在La的情况下是不存在的。还研究了La相互转化为4a的立体化学方面。毫不奇怪，甲醇钠对La环氧杂环的亲核开环应以SN2方式进行，并在1，4-位发生反转。这种转化具有很高的区域选择性，这可能反映了在甲氧基结合之前，苄基C-0减弱的倾向；即加成
Further confirmation that attack of methoxideion at the benzylic Cl and C-4 positions of la prevailsto give 4a was also obtained. The ditosylate 4b was prepared from the diol 4a, and the relevant NMR spectral features characteristic of the latter are retained. Upon treatment with potassium feri-butoxide, 4b is converted to a dimethyl ether identical in all respects with an authentic sample of 1, 4-dimethoxynaphthalene (9). It is noteworthy that naphthalene oxide 2, in contrast to la, undergoes ring-opening at the 2-position by meth-oxide ion and other nucleophiles. 5 This may be attributed to the added allylic character at the C-2 position, which is absent in the case of la.The stereochemical aspects of the interconversion of la to 4a were also studied. It is not surprising that nucleo-philic opening of the oxirane rings of la by sodium methoxide should occur in an SN2 manner with inversion at the 1, 4-positions. That the transformation is highly regioselective may reflect the propensity for benzyl C-0 weakening to precede methoxide binding; ie, the addition