A Facile and Versatile Approach to Double N-Heterohelicenes: Tandem Oxidative C-N Couplings of N-Heteroacenes via Cruciform Dimers
A Facile and Versatile Approach to Double N-Heterohelicenes: Tandem Oxidative C-N Couplings of N-Heteroacenes via Cruciform Dimers
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DOI：
10.1002/anie.201500684
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发表时间：
2015-04-27
影响因子：
16.6
通讯作者：
Seki, Shu
中科院分区：
文献类型：
--
作者：
Sakamaki, Daisuke;Kumano, Daisuke;Seki, Shu
通过氧化偶联的方法，合成了由两个氮取代并杂五苯组成的新型双N-杂[5]螺烯。所开发的方法是非常容易的，使合成的双螺烯在只有两个步骤，从市售的萘衍生物。这些双N-杂[5] helicenes有较大的扭转角在峡湾地区比典型的[5] helicenes，和光学/电化学测量显示，显着增加的电子通信的两个heteropentacene部分的双helicenes相比，其十字形二聚体。对其中一个双螺烯进行了光学拆分，其消旋稳定性明显高于典型的[5]螺烯。本文提出的合成策略是通用的，广泛适用于从其他含N的p-共轭平面分子制备双螺旋烯。
Novel double N-hetero[5] helicenes that are composed of two nitrogen-substituted heteropentacenes are synthesized by tandem oxidative C - N couplings via the cruciform heteropentacene dimers. The developed method is very facile and enables the synthesis of a double helicene in only two steps from commercially available naphthalene derivatives. These double N-hetero[5] helicenes have larger torsion angles in the fjord regions than typical [5] helicenes, and optical/electrochemical measurements revealed a significant increase in the electronic communication between the two heteropentacene moieties of the double helicenes compared with their cruciform dimers. The optical resolution of one of the double helicenes was successfully carried out, and their stability towards racemization was remarkably higher than those of typical [5] helicenes. The synthetic strategy proposed in this paper should be versatile and widely applicable to the preparation of double helicenes from other N-containing p-conjugated planar molecules.