meso-Free Corroles: Syntheses, Structures, Properties, and Chemical Reactivities
meso-Free Corroles: Syntheses, Structures, Properties, and Chemical Reactivities
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无内消旋科罗勒：合成、结构、性质和化学反应性
DOI：
10.1002/chem.201500894
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发表时间：
2015
期刊：
影响因子：
--
通讯作者：
Takayuki Tanaka and Atsuhiro Osuka
中科院分区：
文献类型：
--
作者：
Shota Ooi;Tomoki Yoneda;Takayuki Tanaka and Atsuhiro Osuka
通过合理的合成路线，合成了5，10-二（五氟苯基）咔咯（5）和5，15-二（五氟苯基）咔咯（9）。这两种化合物的结构都通过X射线衍射分析明确地揭示出来，并研究了它们的光学和电化学性质。已经探索了5和9的氯化和氧化二聚，这揭示了5和9中的自由中位的显著不同的反应性。在1%吡啶存在下，9与帕劳氯反应可有效地制备10-氯代可罗莱11，而5的类似氯化可罗莱12可获得痕量的5-氯代可罗莱12。5与AgNO 2反应生成5，5 ′-连接的咔咯二聚体13，产率较高; 9与[双（三氟乙酰氧基）碘]苯反应生成10，10 ′-连接的咔咯二聚体14，产率中等。与14相比，13中两个配体之间观察到的较大的电子相互作用主要归因于前者的构象柔性，这允许更多的共面构象。
5,10‐Bis(pentafluorophenyl)corrole (5) and 5,15‐bis(pentafluorophenyl)corrole (9) have been synthesized asmeso‐free corroles by rational synthetic routes. Both the structures of these corroles have been unambiguously revealed by X‐ray diffraction analysis and their optical and electrochemical properties have been studied. Chlorination and oxidative dimerization of5and9have been explored, which revealed a marked different reactivity of the freemeso‐positions in5and9. 10‐Chlorinated corrole11was effectively prepared by the reaction of9with Palau‘chlor in the presence of 1 % pyridine whereas 5‐chlorinated corrole12was obtained in a trace amount from similar chlorination of5. 5,5′‐Linked corrole dimer13was produced by reaction of5with AgNO2in a good yield, whereas 10,10′‐linked corrole dimer14was formed in a moderate yield by the reaction of9with [bis(trifluoroacetoxy)iodo]benzene. Observed large electronic interaction between the two corroles in13as compared with that in14has been ascribed mainly to conformational flexibility of the former, which allows more coplanar conformation.