Tian Dong, Pan Yixing, Zhao Xiaowei, Yin Yanli, Jiang Zhiyong
Pingyuan Laboratory, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007, P. R. China.
College of pharmacy, Henan University, Kaifeng, Henan 475004, P. R. China.
J Am Chem Soc. 2025 Apr 16;147(15):12410-12417. doi: 10.1021/jacs.5c03542. Epub 2025 Apr 2.
We present an asymmetric intramolecular [2 + 2] photocycloaddition reaction enabled by a dual catalyst system involving DPZ as a photosensitizer and chiral Sc(III) complex, leading to azaarene-functionalized 2-azabicyclo[2.2.1]hexanes (aza-BCHs). The approach efficiently preventing racemization during subsequent nitrogen-deletion skeletal editing of aza-BCHs to yield 2-substituted bicyclo[1.1.1]pentanes (BCPs). The method achieves high ee and broad substrate scope, including the successful formation of all-carbon quaternary stereocenters. Furthermore, the successful activation of simple azaarene substrates by chiral Lewis acids in asymmetric photocatalysis highlights a notable contribution to this field.
我们展示了一种由双催化剂体系实现的不对称分子内[2 + 2]光环加成反应，该体系涉及作为光敏剂的DPZ和手性Sc(III)配合物，生成氮杂芳烃官能化的2-氮杂双环[2.2.1]己烷（氮杂-BCHs）。该方法有效地防止了氮杂-BCHs在随后的脱氮骨架编辑过程中的外消旋化，从而生成2-取代的双环[1.1.1]戊烷（BCPs）。该方法实现了高对映体过量和广泛的底物范围，包括成功形成全碳季立体中心。此外，手性路易斯酸在不对称光催化中成功激活简单的氮杂芳烃底物，突出了对该领域的显著贡献。
