Facile Synthesis and Chiral Resolution of Expanded Helicenes with up to 35 <i>cata</i> ‐Fused Benzene Rings**
Facile Synthesis and Chiral Resolution of Expanded Helicenes with up to 35 <i>cata</i> ‐Fused Benzene Rings**
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具有高达 35 个 <i>cata</i> 稠合苯环的扩展螺旋烯的简便合成和手性拆分**
DOI：
10.1002/anie.202218090
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Wu Jishan
中科院分区：
文献类型：
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作者：
Huo Gui‐Fei;Fukunaga Toshiya M.;Hou Xudong;Han Yi;Fan Wei;Wu Shaofei;Isobe Hiroyuki;Wu Jishan
与经典的螺旋烯相比，膨胀的螺旋烯预期显示出增强的手性光学性质，但是合成是非常具有挑战性的。本文报道了一系列含11、19、27和35个阳离子稠合苯环的扩链螺烯Hn（n=1-4）的简便合成方法。它们的结构通过X射线晶体学分析确定。对映体H2、H3和H4可以通过手性HPLC分离，它们都表现出强的手性响应，具有高的吸收不对称因子（|Gabs|）值（H2为0.020，H3为0.021，H4为0.021-0.024）。
Expanded helicenes are expected to show enhanced chiroptical properties as compared to the classical helicenes but the synthesis is very challenging. Herein, we report the facile synthesis of a series of expanded helicenesHn(n=1–4) containing 11, 19, 27 and 35cata‐fused benzene rings through Suzuki coupling‐based oligomerization followed by Bi(OTf)3‐mediated regioselective cyclization of vinyl ethers. Their structures were determined by X‐ray crystallographic analysis. EnantiopureH2,H3, andH4can be isolated by chiral HPLC and they all exhibit strong chiroptical responses with high absorption dissymmetry factor (|gabs|) values (0.020 forH2, 0.021 forH3, and 0.021–0.024 forH4).