Clarke Aimee K, Parkin Alison, Taylor Richard J K, Unsworth William P, Rossi-Ashton James A
Department of Chemistry, University of York, Heslington, York YO10 5DD, U.K.
ACS Catal. 2020 May 15;10(10):5814-5820. doi: 10.1021/acscatal.0c00690. Epub 2020 Apr 17.
The photocatalytic deoxygenation of sulfoxides to generate sulfides facilitated by either Ir[(dF(CF)ppy)(dtbbpy)]PF or -Ir(ppy) is reported. Mechanistic studies indicate that a radical chain mechanism operates, which proceeds via a phosphoranyl radical generated from a radical/polar crossover process. Initiation of the radical chain was found to proceed via two opposing photocatalytic quenching mechanisms, offering complementary reactivity. The mild nature of the radical deoxygenation process enables the reduction of a wide range of functionalized sulfoxides, including those containing acid-sensitive groups, in typically high isolated yields.
据报道，由Ir[(dF(CF)ppy)(dtbbpy)]PF或-Ir(ppy)促进的亚砜光催化脱氧生成硫化物的反应。机理研究表明，存在一种自由基链机制，该机制通过自由基/极性交叉过程产生的磷酰基自由基进行。发现自由基链的引发通过两种相反的光催化猝灭机制进行，提供了互补的反应性。自由基脱氧过程的温和性质使得能够还原多种官能化亚砜，包括那些含有酸敏感基团的亚砜，通常能以高分离产率得到产物。
