配体控制的芳炔 C1 插入反应构建菲啶酮和吖啶酮生物碱。
Ligand Controlled Regiodivergent C1 Insertion on Arynes for Construction of Phenanthridinone and Acridone Alkaloids.
机构信息
Shanghai Key Laboratory of Green Chemistry and Chemical Process, School of Chemistry and Molecular Engineering, East China Normal University, 3663N, Zhongshan Road, Shanghai, 200062 (P.R. China).
School of Pharmacy, Shanghai University of Traditional Chinese Medicine, Cai Lun Lu 1200, Shanghai, 201203 (P.R. China).
出版信息
Angew Chem Int Ed Engl. 2015 Dec 1;54(49):14960-4. doi: 10.1002/anie.201508340. Epub 2015 Oct 19.
A palladium-catalyzed regiodivergent C1 insertion multicomponent reaction involving aryne, CO, and 2-iodoaniline is established to construct the scaffolds of phenanthridinone and acridone alkaloids. Regioselective control is achieved under the guidance of selective ligands. The phenanthridinones are solely obtained under ligand-free condition. In comparison, application of the electron-abundant bidentate ligand dppm afforded the acridones with high efficiency. The release rate of the aryne from the precursor assists the regioselectivity of insertion as well, which was revealed through interval NMR tracking. A plausible mechanism was suggested based on the control experiments. Representative natural products and two types of natural product analogues were synthesized divergently through this tunable method.
钯催化的 C1 插入多组分反应涉及芳炔、CO 和 2-碘苯胺，用于构建菲啶酮和吖啶酮生物碱的支架。在选择性配体的指导下实现了区域选择性控制。在无配体条件下仅获得菲啶酮。相比之下，应用富电子双齿配体 dppm 可高效获得吖啶酮。通过间隔 NMR 跟踪揭示了芳炔从前体中的释放速率也有助于插入的区域选择性。根据控制实验提出了一个合理的机制。通过这种可调方法，合成了具有代表性的天然产物和两种类型的天然产物类似物。
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