Levernier Etienne, Jaouadi Khaoula, Zhang Heng-Rui, Corcé Vincent, Bernard Aurélie, Gontard Geoffrey, Troufflard Claire, Grimaud Laurence, Derat Etienne, Ollivier Cyril, Fensterbank Louis
Sorbonne Université, CNRS, Institut Parisien de Chimie Moléculaire, 4 Place Jussieu, CC 229, 75252, Paris, France.
Laboratoire de biomolécules (LBM), Département de Chimie, Sorbonne Université, École Normale Supérieure, PSL University, CNRS, 75005, Paris, France.
Chemistry. 2021 Jun 16;27(34):8782-8790. doi: 10.1002/chem.202100453. Epub 2021 May 21.
While the generation of aryl radicals by photoredox catalysis under reductive conditions is well documented, it has remained challenging under an oxidative pathway. Because of the easy photo-oxidation of alkyl bis-catecholato silicates, a general study of phenyl silicates bearing substituted catecholate ligands has been achieved. The newly synthesized phenyl silicates have been fully characterized, and their reactivity has been explored. It was found that, thanks to the substitution of the catecholate moiety, notably with the 4-cyanocatecholato ligand, the phenyl radical could be generated and trapped. Computational studies provided a rationale for these findings.
虽然在还原条件下通过光氧化还原催化生成芳基自由基已有充分记载，但在氧化途径下仍具有挑战性。由于烷基双儿茶酚硅酸酯容易发生光氧化，因此对带有取代儿茶酚配体的苯基硅酸酯进行了全面研究。新合成的苯基硅酸酯已得到充分表征，并对其反应活性进行了探索。结果发现，由于儿茶酚部分的取代，特别是用4-氰基儿茶酚配体取代，苯基自由基能够生成并被捕获。计算研究为这些发现提供了理论依据。
