A Simple Hybrid Cyclyne Consisting of 1,3-Diethynylbenzene and Ether Units: Synthesis and Novel Ag+-Induced Cyclization Leading to the Perylene Skeleton Formation
A Simple Hybrid Cyclyne Consisting of 1,3-Diethynylbenzene and Ether Units: Synthesis and Novel Ag+-Induced Cyclization Leading to the Perylene Skeleton Formation
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由 1,3-二乙炔基苯和醚单元组成的简单杂化环炔：合成和新型银诱导环化导致苝骨架形成
DOI：
10.1021/ja000822w
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发表时间：
2000
期刊：
影响因子：
--
通讯作者：
Z. Yoshida
中科院分区：
文献类型：
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作者：
Y. Yamaguchi;Shigeya Kobayashi;T. Wakamiya;A. Matsubara;Z. Yoshida
结构明确的大环化合物1由于其独特的性质（如特异性识别、选择性结合和络合作用）以及由此产生的分子功能而继续吸引着许多研究小组的浓厚兴趣。作为这样一种大环化合物，我们对一类新的杂化环炔化合物（1）产生了浓厚的兴趣，该类化合物由1，3-二乙炔基苯单元和醚单元组成，具有三种给体基团，具有较大的空腔（n> 3），有望与各种底物形成功能性超分子配合物。另一方面，该家族的简单成员2（n）1）和3（n）2）除了与过渡金属形成预期的络合物之外，由于键角应变2，引起了对结构和反应行为的特别兴趣。我们在这里报告的合成和新的Ag+诱导的高选择性环化3以及尝试合成2。基于2和3的MM 2结构，我们选择了Pd介导的间二碘苯与乙炔在CuI和吡咯烷存在下的偶联反应。3间二碘苯和炔丙基醚的一步合成策略没有得到2和/或3，而是得到低聚物。如方案1所示，威廉姆森由二醇4和相应的二溴化物5合成醚，以约20%的产率提供无色非荧光晶体3。4
Structurally well-defined macrocycles1 continue to attract strong interest from many research groups, because of the emerging unique properties (such as specific recognition, selective binding, and complexation) and the resulting molecular functions. As such a macrocycle, we have been interested in a novel family of hybrid cyclynes (1) consisting of 1, 3-diethynylbenzene units and ether units, which have three kinds of donor groups.The hybrid cyclynes (nanomolecules) having a larger cavity (n> 3) are expected to form functional supramolecular complexes with various substrates. On the other hand, the simple members, 2 (n) 1) and 3 (n) 2), of this family arouse special interest in structure and reaction behavior owing to bond angle strain, 2 besides the expected complex formation with transition metals. We report here synthesis and novel Ag+-induced highly selective cyclization of 3 as well as an attempted synthesis of 2. On the basis of the MM2 structure for 2 and 3, we chose the Pd-mediated coupling reaction of m-diiodobenzene with acetylenes in the presence of CuI and pyrrolidine. 3 The single step synthetic strategy from m-diiodobenzene and propargyl ether did not give 2 and/or 3 but oligomer. As shown in Scheme 1, Williamson’s synthesis of ether from diol 4 and the corresponding dibromide 5 provided 3 as colorless nonfluorescent crystals in around 20% yield. 4