氮化碳光催化羰基键的区域选择性铵自由基加成，生成 N-稠合吡咯。
Carbon nitride photocatalyzes regioselective aminium radical addition to the carbonyl bond and yields N-fused pyrroles.
机构信息
Department of Colloid Chemistry, Max-Planck Institute of Colloids and Interfaces, Research Campus Golm, 14424, Potsdam, Germany.
V.I. Vernadsky Institute of General and Inorganic Chemistry, NAS of Ukraine, Palladina Avenue, 32/34, Kiev, 03142, Ukraine.
出版信息
Nat Commun. 2019 Feb 26;10(1):945. doi: 10.1038/s41467-019-08652-w.
Addition of N-centered radicals to C=C bonds or insertion into C-H bonds is well represented in the literature. These reactions have a tremendous significance, because they afford polyfunctionalized organic molecules. Despite the tetrahydroisoquinoline (THIQ) moiety widely occurring in natural biologically active compounds, N-unsubstituted THIQs as a source of N-centered radicals are not studied. Herein, we report a photocatalytic reaction between tetrahydroisoquinoline and chalcones that gives N-fused pyrroles-1,3-disubstituted-5,6-dihydropyrrolo[2,1-a]isoquinolines (DHPIQ). The mechanism includes at least two photocatalytic events in one pot: (1) C-N bond formation; (2) C-C bond formation. In this process potassium poly(heptazine imide) is used as a visible light active heterogeneous and recyclable photocatalyst. Fifteen N-fused pyrroles are reported with 65-90% isolated yield. DHPIQs are characterized by UV-vis and fluorescence spectroscopy, while the fluorescence quantum efficiency of fluorinated DHPIQs reaches 24%.
在文献中，N 中心自由基与 C=C 键的加成或 C-H 键的插入反应得到了很好的体现。这些反应具有重要意义，因为它们提供了多官能化的有机分子。尽管四氢异喹啉（THIQ）部分广泛存在于天然生物活性化合物中，但 N-未取代的 THIQ 作为 N 中心自由基的来源尚未得到研究。在此，我们报道了四氢异喹啉和查尔酮之间的光催化反应，得到了 N-稠合的吡咯-1,3-二取代-5,6-二氢吡咯并[2,1-a]异喹啉（DHPIQ）。该机理至少包括一锅法中的两个光催化事件：（1）C-N 键形成；（2）C-C 键形成。在这个过程中，聚（六嗪亚胺）钾被用作可见光活性的多相和可回收光催化剂。报道了 15 个 N-稠合的吡咯，产率为 65-90%。DHPIQs 通过紫外-可见和荧光光谱进行了表征，而氟化 DHPIQs 的荧光量子效率达到了 24%。
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