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Regioselective Synthesis of Angular Isocoumarinselenazoles: A Benzoselenazole‐directed, Site‐specific, Ruthenium‐catalyzed C(sp2)‐H Activation
Advanced Synthesis & Catalysis ( IF 4.4 ) Pub Date : 2018-01-12 , DOI: 10.1002/adsc.201701256
Sandip Dhole,Jen-Yu Liao,Sunil Kumar,Deepak B. Salunke,Chung-Ming Sun

The synthesis of new, angular isocoumarinselenazoles is described, which involves the construction of 2‐amino benzoselenazoles and their regioselective C2N‐alkylation and alkyne insertion. An expeditious and metal‐free synthesis of 2‐aminobenzoselenazoles by the reaction of methyl 3‐amino‐4‐fluorobenzoate and isoselenocyanates was achieved. Further N‐alkylation of the 2‐aminobenzoselenazoles resulted the formation of two regioisomers with different reactivities towards the alkyne insertion. The regioselective construction of the α‐pyrone ring on the benzo[1,3‐d]selenazole skeleton was achieved via a ruthenium (II)‐catalyzed oxidative annulation. It is clear that the selenazole nitrogen plays an important role in the observed selectivity.

中文翻译:

角异香豆素烯的区域选择性合成:以苯甲硒唑为导向的,位点特定的,钌催化的C(sp2)-H活化

的新的,角isocoumarinselenazoles的合成所描述的,这涉及2-氨基benzoselenazoles的结构和它们的区域选择性C2 Ñ烷基化和炔插入。通过3-氨基-4-氟代苯甲酸甲酯与异硒烯氰酸酯的快速合成反应而实现了2-氨基苯并硒唑的无金属合成。2-氨基苯并硒唑的进一步N-烷基化导致形成两个区域异构体,这些区域对炔烃的插入具有不同的反应性。苯并[1,3- d ]硒烯唑骨架上α-吡咯环的区域选择性构建是通过钌(II)催化的氧化环化实现的。显然,硒氮唑氮在观察到的选择性中起重要作用。
更新日期:2018-01-12
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