Enantioselective synthesis of [4]helicenes by organocatalyzed intermolecular C-H amination.
Enantioselective synthesis of [4]helicenes by organocatalyzed intermolecular C-H amination.
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DOI：
10.1038/s41467-024-45049-w
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发表时间：
2024-01-25
影响因子：
16.6
通讯作者：
Wang, Rui
中科院分区：
文献类型：
--
作者：
Liu, Xihong;Zhu, Boyan;Zhang, Xiaoyong;Zhu, Hanwen;Zhang, Jingying;Chu, Anqi;Wang, Fujun;Wang, Rui
螺旋手性分子的催化不对称合成仍然是一个突出的挑战，并且在过去几十年中取得的进展相当有限。目前构建此类化合物的方法几乎完全依赖于催化对映体控制的稠环系统延伸。在此，我们报告了一种直接末端周边官能化策略，该策略允许通过2-羟基苯并[c]菲衍生物与重氮二甲酰胺的有机催化的对映选择性胺化反应有效组装1,12-二取代的[4]碳螺旋烯。该方法的关键特点是催化剂的立体化学信息不仅可以转化为产物的螺旋方向，还可以转化为产物的远程C-N轴向手性，从而能够以良好的效率和优异的对映体控制合成具有结构多样性和立体化学复杂性的[4]-和[5]螺旋烯。此外，螺旋产物的大规模制备和代表性转化进一步证明了该方案的实用性。此外，DFT计算表明，底物和催化剂之间的氢键和C-H---π相互作用都有助于理想的立体化学控制。目前构建用于不对称催化的螺旋手性分子的方法几乎完全依赖于催化对映体控制的稠环系统延伸。在此，作者报告了一种直接末端周边官能化策略，该策略允许通过有机催化的对映选择性胺化反应有效组装取代的碳螺旋烯。
Catalytic asymmetric synthesis of helically chiral molecules has remained an outstanding challenge and witnessed fairly limited progress in the past decades. Current methods to construct such compounds almost entirely rely on catalytic enantiocontrolled fused-ring system extension. Herein, we report a direct terminal peri-functionalization strategy, which allows for efficient assembling of 1,12-disubstituted [4]carbohelicenes via an organocatalyzed enantioselective amination reaction of 2-hydroxybenzo[c]phenanthrene derivates with diazodicarboxamides. The key feature of this approach is that the stereochemical information of the catalyst could be transferred into not only the helix sense but also the remote C-N axial chirality of the products, thus enabling the synthesis of [4]- and [5]helicenes with both structural diversity and stereochemical complexity in good efficiency and excellent enantiocontrol. Besides, the large-scale preparations and representative transformations of the helical products further demonstrate the practicality of this protocol. Moreover, DFT calculations reveal that both the hydrogen bonds and the C-H---π interactions between the substrates and catalyst contribute to the ideal stereochemical control. Current methods to construct helical chiral molecules for asymmetric catalysis almost entirely rely on catalytic enantiocontrolled fused-ring system extension. Herein, the authors report a direct terminal peri-functionalization strategy, which allows for efficient assembling of substituted carbohelicenes via an organocatalyzed enantioselective amination reaction.
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