Synthesis of symmetrical polynitrohelicenes and their chiral recognition in the charge transfer complexation.
Synthesis of symmetrical polynitrohelicenes and their chiral recognition in the charge transfer complexation.
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对称聚硝基螺烯的合成及其在电荷转移络合中的手性识别。
DOI：
10.1021/jo001419a
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发表时间：
2001
期刊：
影响因子：
--
通讯作者：
M. Yamaguchi
中科院分区：
文献类型：
--
作者：
H. Okubo;D. Nakano;S. Anzai;M. Yamaguchi
光学活性的1，12-二甲基苯并[c]菲-5，8-二羧酸衍生物可以区域选择性硝化，得到对称多官能化的螺烯。二羧酸或其二甲酯在乙酸中用发烟硝酸在4，9-位进行二硝化。当反应在发烟硝酸中进行时，得到2，4，9，11-四硝基螺烯。类似地，1，12-二甲基苯并[c]菲-5，8-二腈根据条件得到2，11-二硝基-或4，9-二硝基螺烯，并且前一种化合物转化为2，4，9，11-四硝基螺烯。四硝基螺烯在溶液中与富电子手性二氨基螺烯形成电荷转移（CT）复合物。对手性识别的研究表明，相同构型的螺烯组合形成的配合物比对映体螺烯更稳定。
Derivatives of optically active 1,12-dimethylbenzo[c]phenanthrene-5,8-dicarboxylic acid can be nitrated regioselectively, giving symmetrically polyfunctionalized helicenes. The dicarboxylic acid or its dimethyl ester is dinitrated with fuming nitric acid in acetic acid at the 4,9-positions. When the reaction is conducted in fuming nitric acid, a 2,4,9,11-tetranitrohelicene is obtained. Analogously, 1,12-dimethylbenzo[c]phenanthrene-5,8-dinitrile gives 2,11-dinitro- or 4,9-dinitrohelicene depending on the conditions, and the former compound is converted to a 2,4,9,11-tetranitrohelicene. The tetranitrohelicenes form charge-transfer (CT) complexes with an electron-rich chiral diaminohelicene in solution. The studies on the chiral recognition reveal that the combinations of the same configuration of the helicenes form more stable complexes than that of the enantiomeric helicenes.