Angew. Chem. ：Ni(II)催化的Diels−Alder反应/脱水芳构化反应实现三重轴手性萘甲酸酯的对映选择性合成

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 具有多个手性轴的阻转异构体由于其在天然产物、药物分子和材料科学等领域的重要性而备受关注。目前的研究主要集中于在单重轴手性芳环骨架的合成上，而在单个苯环上实现具有双重以上轴手性的芳环骨架的立体选择性构建极具挑战性，这极大地多重轴手性分子在功能分子创制中的应用。


近日，复旦大学化学系蔡泉课题组以1,3-二芳基取代的异苯并呋喃与β-芳基取代的α,β-不饱和N-酰基吡唑为底物，通过Ni(II)催化的Diels−Alder反应和布朗斯特酸促进的脱水芳构化反应，实现了结构新颖的三重轴手性多取代萘的高对映以及非对映选择性合成。基于这些三重轴手性骨架，他们开发了一种具有高glum值(0.019)和ØFL值(0.29)的CPL活性染料。

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通过条件筛选，作者发现在Ni(II)与手性双噁唑啉L1的催化作用下，第一步Diels–Alder反应能够以99%的产率，94%的ee值和15:1的dr值得到产物3a。作者将3a用NaOEt处理转化为相应的羧酸乙酯中间体，随后通过酸和温度的筛选，在三氟甲磺酸的作用下能够以88%的产率，94%的ee和>20:1 dr得到芳构化产物4a。该反应底物普适性良好，各类给电子或吸电子取代基都能够很好的耐受，反应具有较好的对映及非对映选择性控制。

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此外，作者发现，将两个芘环引入到三重轴手性萘骨架得到的化合物16具有非常好的圆偏振发光活性以及较高的荧光量子产率(ØFL = 0.29)。相对于其他常规有机小分子，16有着非常高的发光不对称因子|glum|，约为0.019，从而显示了三重轴手性骨架在手性有机发光材料开发领域的应用潜力。

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论文信息

Enantioselective Synthesis of Atropisomeric Tri-Axis Naphthalenes via Diels–Alder Reaction and Dehydrative Aromatization of Isobenzofurans

Yuan-Bo Du, Qi-Tao Lu, Yun-Shu Cui, Kai-Wen Wu, Dr. Yu Wang, Yu-Zhen Zhang, Prof. Dr. Zheng Zhao, Prof. Dr. Jun-Li Hou, Prof. Dr. Quan Cai


Angewandte Chemie International Edition

DOI: 10.1002/anie.202421060

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