期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 143, 期 33, 页码 13266-13273出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.1c05994
关键词
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资金
- Pharma Innovation Programme Singapore (A* STAR) [SERC A19B3a0014]
- National University of Singapore [R-143000-B60-114]
- National Natural Science Foundation of China [22071170, 21502135]
This article discusses the unprecedented discovery that a family of fluorophores can undergo consecutive photoinduced electron transfer (ConPET) to achieve very high reduction potentials. One of the newly synthesized catalysts can activate reductively recalcitrant aryl chlorides under mild conditions, producing valuable organic synthesis products.
Since the seminal work of Zhang in 2016, donor-acceptor cyanoarene-based fluorophores, such as 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN), have been widely applied in photoredox catalysis and used as excellent metal-free alternatives to noble metal Ir- and Ru-based photocatalysts. However, all the reported photoredox reactions involving this chromophore family are based on harnessing the energy from a single visible light photon, with a limited range of redox potentials from -1.92 to +1.79 V vs SCE. Here, we document the unprecedented discovery that this family of fluorophores can undergo consecutive photoinduced electron transfer (ConPET) to achieve very high reduction potentials. One of the newly synthesized catalysts, 2,4,5-tri(9H-carbazol-9-yl)-6-(ethyl(phenyl)amino)isophthalonitrile (3CzEPAIPN), possesses a long-lived (12.95 ns) excited radical anion form, 3CzEPAIPN(center dot-)*, which can be used to activate reductively recalcitrant aryl chlorides (E-red approximate to -1.9 to -2.9 V vs SCE) under mild conditions. The resultant aryl radicals can be engaged in synthetically valuable aromatic C-B, C-P, and C-C bond formation to furnish arylboronates, arylphosphonium salts, arylphosphonates, and spirocyclic cyclohexadienes.
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