Iron and Manganese Catalysts for the Selective Functionalization of Arene C(sp2)−H Bonds by Carbene Insertion

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• 作者：Dr. Ana Conde ; Gerard Sabenya ; Mò ; nica Rodrí ; guez ; Verò ; nica Postils ; Dr. Josep M. Luis ; Dr. M. Mar Dí ; az-Requejo ; Dr. Miquel Costas and Prof. Dr. Pedro J. Pé ; rez
• 刊名：Angewandte Chemie International Edition
• 出版年：2016
• 出版时间：May 23, 2016
• 年：2016
• 卷：55
• 期：22
• 页码：6530-6534
• 全文大小：755K
• ISSN：1521-3773

文摘

The first examples of the direct functionalization of non-activated aryl sp² C−H bonds with ethyl diazoacetate (N₂CHCO₂Et) catalyzed by Mn- or Fe-based complexes in a completely selective manner are reported, with no formation of the frequently observed cycloheptatriene derivatives through competing Buchner reaction. The best catalysts are Fe^II or Mn^II complexes bearing the tetradentate pytacn ligand (pytacn= 1-(2-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane). When using alkylbenzenes, the alkylic C(sp³)−H bonds of the substituents remained unmodified, thus the reaction being also selective toward functionalization of sp² C−H bonds.