Selective Radical Amination of Aldehydic C(sp(2))-H Bonds with Fluoroaryl Azides via Co(II)-Based Metalloradical Catalysis: Synthesis of N-Fluoroaryl Amides from Aldehydes under Neutral and Nonoxidative Conditions.
Selective Radical Amination of Aldehydic C(sp(2))-H Bonds with Fluoroaryl Azides via Co(II)-Based Metalloradical Catalysis: Synthesis of N-Fluoroaryl Amides from Aldehydes under Neutral and Nonoxidative Conditions.
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DOI：
10.1039/c4sc00697f
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发表时间：
2014-06-01
期刊：
影响因子：
8.4
通讯作者：
Zhang XP
中科院分区：
文献类型：
--
作者：
Jin LM;Lu H;Cui Y;Lizardi CL;Arzua TN;Wojtas L;Cui X;Zhang XP
D2 h对称氨基卟啉3，5-DitBu-IbuPhyrin的Co（II）配合物[Co（P1）]已被证明是一种有效的金属自由基催化剂，用于醛与氟代芳基叠氮化合物的C（sp2）-H键的分子间胺化。[Co（P1）]催化的过程可以采用醛作为限制试剂，并在中性和非氧化条件下操作，产生氮气作为唯一的副产物。金属自由基的C-H胺化反应适用于醛和氟代芳基叠氮化物的不同组合，以良好至优异的产率产生相应的N-氟代芳基酰胺。一系列的机理研究支持逐步自由基机理的Co（II）催化的分子间C-H胺化。
The Co(II) complex of the D2h-symmetric amidoporphyrin 3,5-DitBu-IbuPhyrin, [Co(P1)], has proven to be an effective metalloradical catalyst for intermolecular amination of C(sp2)–H bonds of aldehydes with fluoroaryl azides. The [Co(P1)]-catalyzed process can employ aldehydes as the limiting reagents and operate under neutral and non-oxidative conditions, generating nitrogen gas as the only byproduct. The metalloradical aldehydic C–H amination is suitable for different combinations of aldehydes and fluoroaryl azides, producing the corresponding N-fluoroaryl amides in good to excellent yields. A series of mechanistic studies support a stepwise radical mechanism for the Co(II)-catalyzed intermolecular C–H amination.