Schmalzbauer Matthias, Marcon Michela, König Burkhard
Faculty of Chemistry and Pharmacy, University of Regensburg, Universitätsstrasse 31, 93053, Regensburg, Germany.
Angew Chem Int Ed Engl. 2021 Mar 15;60(12):6270-6292. doi: 10.1002/anie.202009288. Epub 2020 Dec 29.
Utilizing light is a smart way to fuel chemical transformations as it allows the energy to be selectively focused on certain molecules. Many reactions involving electronically excited species proceed via open-shell intermediates, which offer novel and unique routes to expand the hitherto used synthetic toolbox in organic chemistry. The direct conversion of non-prefunctionalized, less activated compounds is a highly desirable goal to pave the way towards more sustainable and atom-economic chemical processes. Photoexcited closed-shell anions have been shown to reach extreme potentials in single electron transfer reactions and reveal unusual excited-state reactivity. It is, therefore, surprising that their use as a reagent or photocatalyst is limited to a few examples. In this Review, we briefly discuss the characteristics of anionic photochemistry, highlight pioneering work, and show recent progress which has been made by utilizing photoexcited anionic species in organic synthesis.
利用光来推动化学转化是一种明智的方式，因为它能使能量有选择地聚焦于某些分子。许多涉及电子激发态物种的反应通过开壳中间体进行，这为扩展有机化学中迄今使用的合成工具箱提供了新颖独特的途径。将未预官能化、活性较低的化合物直接转化是朝着更可持续和原子经济的化学过程迈进的一个非常理想的目标。光激发的闭壳阴离子已被证明在单电子转移反应中能达到极高的电位，并展现出不寻常的激发态反应活性。然而，令人惊讶的是，它们作为试剂或光催化剂的应用仅限于少数例子。在本综述中，我们简要讨论阴离子光化学的特点，突出开创性工作，并展示利用光激发阴离子物种在有机合成中所取得的最新进展。
