Tripathi Chandra Bhushan, Ohtani Tsuyoshi, Corbett Michael T, Ooi Takashi
Institute of Transformative Bio-Molecules (WPI-ITbM) , Department of Molecular and Macromolecular Chemistry , Graduate School of Engineering , Nagoya University , Nagoya 464-8601 , Japan . Email:
CREST , Japan Science and Technology Agency (JST) , Nagoya University , Nagoya 464-8601 , Japan.
Chem Sci. 2017 Aug 1;8(8):5622-5627. doi: 10.1039/c7sc01700f. Epub 2017 Jun 5.
The photoexcited aryl ketone-catalyzed C-H imidation of arenes and heteroarenes is reported. Using 3,6-dimethoxy-9-thioxanthen-9-one as a catalyst in combination with a bench-stable imidating reagent, C-N bond formation proceeds with high efficiency and a broad substrate scope. A key part of this method is that the thioxanthone catalyst acts as an excited-state reductant, thus establishing an oxidative quenching cycle for radical aromatic substitution. The synthetic potential of this photoexcited ketone catalysis is further demonstrated by application to the direct C-H acyloxylation of arenes.
报道了光激发芳基酮催化芳烃和杂芳烃的C-H亚胺化反应。使用3,6-二甲氧基-9-硫代呫吨-9-酮作为催化剂，与一种易于保存的亚胺化试剂相结合，C-N键的形成反应高效进行，且底物范围广泛。该方法的关键在于硫代呫吨酮催化剂作为激发态还原剂，从而建立了一个用于自由基芳香取代的氧化猝灭循环。通过将其应用于芳烃的直接C-H酰氧基化反应，进一步证明了这种光激发酮催化反应的合成潜力。
