Department of Chemistry , University of California , Berkeley , California 94720 , United States.
J Am Chem Soc. 2019 Mar 13;141(10):4308-4315. doi: 10.1021/jacs.8b11273. Epub 2019 Jan 17.
Herein, we report on the photoredox-initiated gold-mediated C(sp)-CF and C(sp)-N coupling reactions. By adopting gold as a platform for probing metallaphotoredox catalysis, we demonstrate that cationic gold(III) complexes are the key intermediates of the C-C and C-N coupling reactions. The high-valent gold(III) intermediates are accessed by virtue of photoredox catalysis through a radical chain process. In addition, the bond-forming step of the coupling reactions is the reductive elimination from cationic gold(III) intermediates, which is supported by isolation and crystallographic characterization of key Au(III) intermediates.
本文报道了光氧化还原引发的金介导的 C(sp)-CF 和 C(sp)-N 偶联反应。通过采用金作为探测金属光氧化还原催化的平台，我们证明了阳离子金(III)配合物是 C-C 和 C-N 偶联反应的关键中间体。高价金(III)中间体是通过光氧化还原催化通过自由基链过程获得的。此外，偶联反应的成键步骤是阳离子金(III)中间体的还原消除，这得到了关键 Au(III)中间体的分离和晶体学表征的支持。
