Journal Article10.1021/JACS.0C00212
Cerium Catalyzed C–H Functionalizations of Alkanes Utilizing Alcohols as Hydrogen Atom Transfer Agents
Qing An,Qing An,Ziyu Wang,Ziyu Wang,Yuegang Chen,Xin Wang,Xin Wang,Kaining Zhang,Kaining Zhang,Hui Pan,Hui Pan,Weimin Liu,Zhiwei Zuo,Zhiwei Zuo +13 more
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TL;DR: The LMCT excitation event has been investigated through a series of spectroscopic experiments, revealing a rapid bond homolysis process and an effective produc-tion of alkoxy radicals, collectively ruling out the LMCT/homolysis event as the rate determining step of this C-H functionalization.
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Abstract: Modern photoredox catalysis has traditionally relied upon metal-to-ligand charge-transfer (MLCT) excitation of metal polypyridyl complexes for the utilization of light energy for the activation of organic substrates. Here, we demonstrate the catalytic application of ligand-to-metal charge-transfer (LMCT) excitation of cerium alkoxide complexes for the facile activation of alkanes utilizing abundant and inexpensive cerium trichloride as the catalyst. As demonstrated by cerium-catalyzed C-H amination and the alkylation of hydrocarbons, this reaction manifold has enabled the facile use of abundant alcohols as practical and selective hydrogen atom transfer (HAT) agents via the direct access of energetically challenging alkoxy radicals. Furthermore, the LMCT excitation event has been investigated through a series of spectroscopic experiments, revealing a rapid bond homolysis process and an effective production of alkoxy radicals, collectively ruling out the LMCT/homolysis event as the rate-determining step of this C-H functionalization.
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Citations
Photoredox-Catalyzed C-H Functionalization Reactions.
TL;DR: The use of photoredox catalysis in C-H functionalization reactions has garnered enormous interest and utility in the past several decades as discussed by the authors, including natural product synthesis, drug discovery, radiolabeling, bioconjugation, materials, and fine chemical synthesis.
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Photons or Electrons? A Critical Comparison of Electrochemistry and Photoredox Catalysis for Organic Synthesis.
TL;DR: In this paper, the authors highlight the differences and similarities between electrochemistry and photoredox catalysis by comparing their underlying physical chemistry principles and describing their impact on electrochemical and photochemical methods.
330
Photoinduced intermolecular hydrogen atom transfer reactions in organic synthesis
Hui Cao,Xinxin Tang,Haidi Tang,Ye Yuan,Jie Wu +4 more
- 19 Aug 2021
TL;DR: Recently, photo-induced intermolecular HAT reactions have seen substantial development of their versatility, efficiency, and selectivity, and a recent review summarizes recent advances in this rapidly expanding research area as mentioned in this paper.
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Visible-Light-Induced Homolysis of Earth-Abundant Metal-Substrate Complexes: A Complementary Activation Strategy in Photoredox Catalysis.
TL;DR: In this paper, the authors proposed the visible-light-induced homolysis (VLIH) process, which involves the formation of suitable light-absorbing ligated metal-substrate complexes (Mn Ln -Z; Z=substrate) that can undergo homolytic cleavage to generate Mn-1 Ln and Z for further transformations.
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Photocatalytic Late-Stage C-H Functionalization.
TL;DR: A review of photocatalytic late-stage C-H functionalization strategies for small molecule drugs, agrochemicals, and natural products can be found in this article .
271
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