Li Jie, John Michael, Ackermann Lutz
Institut für Organische und Biomolekulare Chemie, Georg-August-Universität, Tammannstrasse 2, 37077 Göttingen (Germany), Fax: (+49) 551-39-6777.
Chemistry. 2014 Apr 25;20(18):5403-8. doi: 10.1002/chem.201304944. Epub 2014 Mar 27.
Cationic ruthenium complexes derived from KPF6 or AgOAc enabled efficient oxidative CH functionalizations on aryl and heteroaryl amidines. Thus, oxidative annulations of diversely decorated internal alkynes provided expedient access to 1-aminoisoquinolines, while catalyzed C-H activations with substituted acrylates gave rise to structurally novel 1-iminoisoindolines. The powerful ruthenium(II) catalysts displayed a remarkably high site-, regio- and, chemoselectivity. Therefore, the catalytic system proved tolerant of a variety of important electrophilic functional groups. Detailed mechanistic studies provided strong support for the cationic ruthenium(II) catalysts to operate by a facile, reversible C-H activation.
由KPF6或AgOAc衍生的阳离子钌配合物能够在芳基和杂芳基脒上实现高效的氧化C-H官能化。因此，对各种修饰的内炔进行氧化环化可方便地得到1-氨基异喹啉，而用取代丙烯酸酯催化的C-H活化则产生了结构新颖的1-亚氨基异吲哚啉。强大的钌(II)催化剂表现出非常高的位点、区域和化学选择性。因此，该催化体系被证明对多种重要的亲电官能团具有耐受性。详细的机理研究为阳离子钌(II)催化剂通过简便、可逆的C-H活化进行反应提供了有力支持。
