复旦大学蔡泉团队报道了Diels-Alder反应和异苯并呋喃脱水芳构化，对映选择性合成消旋异构体三轴萘。相关研究成果发表在2024年12月9日出版的《德国应用化学》。

具有多个立体轴的消旋异构体，因其在天然产物、手性材料和药物发现领域的重要性日益增加，而引起了人们的广泛关注。然而，在单个苯环上具有两个以上轴的轴向手性环支架的催化立体选择性构建，仍然是一项具有挑战性的任务。

该文中，研究人员提出了一种通过异苯并呋喃的顺序Ni（II）催化Diels-Alder反应，和TfOH促进的脱水芳构化反应，合成三轴手性多取代萘支架的有效方法。

研究人员以1，3-二芳基异苯并呋喃和β-芳基取代的α，β-不饱和N-酰基吡唑为模块化反应伙伴，合成了一系列具有1，3，4-三羟基的萘，其具有优异的对映选择性和非对映选择性。

此外，研究人员通过将两个芘发色团附着在，这种新型的三轴手性环支架上，获得了一种具有显著发光不对称因子（glum=0.019），和高荧光量子效率（FL=0.29）的圆偏振发光（CPL）活性染料，突显了具有多个立体轴的阻转异构体，在手性有机材料设计中的潜在应用。

附：英文原文

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

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

Issue&Volume: 2024-12-09

Abstract: Atropisomers with multiple stereogenic axes have attracted much attention due to their increasing significance in the fields of natural products, chiral materials, and drug discoveries. However, the catalytic stereoselective construction of axially chiral ring scaffolds with more than two axes on a single benzene ring remains a challenging task. Herein, we present an efficient method for synthesizing triaxially chiral polysubstituted naphthalene scaffolds via sequential Ni(II)-catalyzed Diels–Alder reaction of isobenzofurans and TfOH-promoted dehydrative aromatization reaction. Using 1,3-biarylisobenzofurans and β-aryl-substituted α,β-unsaturated N-acyl pyrazoles as modular reaction partners, a series of naphthalenes with 1,3,4-triaxes were synthesized with excellent enantioselectivities and diastereoselectivities. Furthermore, by attaching two pyrene chromophores to this novel triaxially chiral ring scaffold, a circularly polarized luminescence (CPL)-active dye exhibiting a remarkable luminescence dissymmetry factor (glum = 0.019) and high fluorescence quantum efficiency (FL = 0.29) was obtained, highlighting the potential applications of atropisomers with multiple stereogenic axes in the design of chiroptical organic materials.

DOI: 10.1002/anie.202421060

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202421060