Váňa Lubomír, Jakubec Martin, Sýkora Jan, Císařová Ivana, Žádný Jaroslav, Storch Jan, Církva Vladimír
Department of Inorganic Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030, 128 40 Prague 2, Czech Republic.
J Org Chem. 2022 Jun 3;87(11):7150-7166. doi: 10.1021/acs.joc.2c00375. Epub 2022 May 12.
A series of aza[]helicenes ( = 4-7) was synthesized using a photocyclodehydrochlorination of 1-chloro--aryl-2-naphthamides as a general synthetic procedure introducing the nitrogen atom to the third ring of the helicene framework. The effect of the nitrogen presence in the helicene skeleton on the physicochemical properties of the prepared aza[]helicenes was studied and compared to those of the parent carbo-analogues. The insertion of a nitrogen atom into the outer edge of the helicene molecule has a severe impact on certain physicochemical properties such as optical rotation, electrostatic potentials, and intermolecular interactions. On the other hand, some other properties such as UV/vis, fluorescence, and phosphorescence spectra remained almost unaffected when compared to the parent carbohelicenes. A nitrogen atom can be also used for further derivatization, which can lead to further modification of helicene properties, as manifested here in the fluorescence changes induced by protonation.
通过1-氯-α-芳基-2-萘酰胺的光环化脱氯化氢反应，合成了一系列氮杂[ ]螺旋烯（ = 4 - 7），这是一种将氮原子引入螺旋烯骨架第三环的通用合成方法。研究了螺旋烯骨架中氮的存在对所制备的氮杂[ ]螺旋烯物理化学性质的影响，并与母体碳类似物进行了比较。在螺旋烯分子的外边缘插入一个氮原子对某些物理化学性质有严重影响，如旋光性、静电势和分子间相互作用。另一方面，与母体碳螺旋烯相比，一些其他性质如紫外/可见光谱、荧光光谱和磷光光谱几乎不受影响。氮原子还可用于进一步衍生化，这可能导致螺旋烯性质的进一步修饰，如这里质子化诱导的荧光变化所示。
