Visible Light-Mediated Atom Transfer Radical Addition via Oxidative and Reductive Quenching of Photocatalysts

详细信息    查看全文

• 作者：Carl-Johan Wallentin ; John D. Nguyen ; Peter Finkbeiner ; Corey R. J. Stephenson
• 刊名：The Journal of the American Chemical Society
• 出版年：2012
• 出版时间：May 30, 2012
• 年：2012
• 卷：134
• 期：21
• 页码：8875-8884
• 全文大小：671K
• 年卷期：v.134,no.21(May 30, 2012)
• ISSN：1520-5126

文摘

Herein, the development of visible light-mediated atom transfer radical addition (ATRA) of haloalkanes onto alkenes and alkynes using the reductive and oxidative quenching of [Ir{dF(CF₃)ppy}₂(dtbbpy)]PF₆ and [Ru(bpy)₃]Cl₂ is presented. Initial investigations indicated that the oxidative quenching of photocatalysts could effectively be utilized for ATRA, and since that report, the protocol has been expanded by broadening the scope of the reaction in terms of the photocatalysts, substrates, and solvents. In addition, further modifications of the reaction conditions allowed for the efficient ATRA of perfluoroalkyl iodides onto alkenes and alkynes utilizing the reductive quenching cycle of [Ru(bpy)₃]Cl₂ with sodium ascorbate as the sacrificial electron donor. These results signify the complementary nature of the oxidative and reductive quenching pathways of photocatalysts and the ability to predictably direct reaction outcome through modification of the reaction conditions.