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通过六边形和七边形环连接的芘稠合[7]螺旋烯:立体专一性合成与手性光学性质

Pyrene-Fused [7]Helicenes Connected Via Hexagonal and Heptagonal Rings: Stereospecific Synthesis and Chiroptical Properties.

作者信息

Swain Asim Kumar, Radacki Krzysztof, Braunschweig Holger, Ravat Prince

机构信息

Institut für Organische Chemie, Universität Würzburg, D-97074 Würzburg, Germany.

Institut für Anorganische Chemie, Universität Würzburg, D-97074 Würzburg, Germany.

出版信息

J Org Chem. 2022 Jan 21;87(2):993-1000. doi: 10.1021/acs.joc.1c02281. Epub 2022 Jan 6.

Abstract

In this manuscript, we portrayed a stereospecific synthesis of - and -symmetric pyrene-fused [7]helicene compounds and , respectively. Compounds and were synthesized via a one-pot Suzuki coupling-C-H activation and two-step Suzuki coupling-Scholl reaction, respectively, with complete retention of configuration. The synthesized molecules differ in the fusing mode of [7]helicene units with pyrene via six- and seven-membered rings for and , respectively. There was a significant difference in the functional properties and enantiomerization barrier of both compounds because of their distinct molecular symmetry as well as fusing mode to pyrene moiety. The heptagon-containing molecule showed remarkable photophysical and chiroptical properties with commendable configurational stability compared to and pristine [7]helicene as well as its [5]helicene congener.

摘要

在本手稿中,我们分别描述了 - 和 - 对称的芘稠合[7]螺旋烯化合物 和 的立体专一合成。化合物 和 分别通过一锅法铃木偶联 - C - H活化和两步铃木偶联 - 肖尔反应合成,构型完全保留。合成的分子在[7]螺旋烯单元与芘的稠合模式上有所不同, 是通过六元环, 是通过七元环。由于这两种化合物具有独特的分子对称性以及与芘部分的稠合模式,它们的功能性质和对映异构化势垒存在显著差异。与 、原始[7]螺旋烯及其[5]螺旋烯同系物相比,含七元环的分子 表现出显著的光物理和手性光学性质以及值得称赞的构型稳定性。

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