A General Organocatalytic System for Electron Donor-Acceptor Complex Photoactivation and Its Use in Radical Processes.
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TL;DR: In this paper, a modular class of organic catalysts acting as donors can readily form photoactive electron donor-acceptor (EDA) complexes with a variety of radical precursors.
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Abstract: We report herein a modular class of organic catalysts that, acting as donors, can readily form photoactive electron donor-acceptor (EDA) complexes with a variety of radical precursors. Excitation with visible light generates open-shell intermediates under mild conditions, including nonstabilized carbon radicals and nitrogen-centered radicals. The modular nature of the commercially available xanthogenate and dithiocarbamate anion organocatalysts offers a versatile EDA complex catalytic platform for developing mechanistically distinct radical reactions, encompassing redox-neutral and net-reductive processes. Mechanistic investigations, by means of quantum yield determination, established that a closed catalytic cycle is operational for all of the developed radical processes, highlighting the ability of the organic catalysts to turn over and iteratively drive every catalytic cycle. We also demonstrate how the catalysts' stability and the method's high functional group tolerance could be advantageous for the direct radical functionalization of abundant functional groups, including aliphatic carboxylic acids and amines, and for applications in the late-stage elaboration of biorelevant compounds and enantioselective radical catalysis.
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Citations
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
Sustainable Thioetherification via Electron Donor-Acceptor Photoactivation using Thianthrenium Salts.
TL;DR: This work describes an open-to-air, photoinduced, site-selective C-H thioetherification from readily available reagents via EDA complex formation, tolerating a wide range of different functional groups.
128
A general electron donor–acceptor complex for photoactivation of arenes via thianthrenation
TL;DR: In this paper , photoactivation of electron donor-acceptor (EDA) complexes between arylsulfonium salts and 1,4-diazabicyclo[2.2] octane with visible light or natural sunlight was discovered.
Arenethiolate as a Dual Function Catalyst for Photocatalytic Defluoroalkylation and Hydrodefluorination of Trifluoromethyls
Can Liu,Kang-Nan Li,Rui Shang +2 more
TL;DR: In this article , an arene thiolate with an appropriate substituent can be photoactivated under visible light to function as both a strongly reducing electron-donating redox catalyst and a HAT catalyst to enable catalytic C-F activation of trifluoromethyl substrates.
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References
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TL;DR: Mechanistic studies revealed a likely radical chain process via the formation of a dearomatized intermediate, providing a deeper understanding of the factors governing the reactivity of these radical forebears, proving its applicability.
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Deaminative Borylation of Aliphatic Amines Enabled by Visible Light Excitation of an Electron Donor–Acceptor Complex
TL;DR: A deaminative strategy for the borylation of aliphatic primary amines is described and the synthetic potential of this mild protocol was demonstrated through the late-stage functionalization of natural products and drug molecules.
X-Ray Characterization of an Electron Donor–Acceptor Complex that Drives the Photochemical Alkylation of Indoles†
Sandeep R. Kandukuri,Ana Bahamonde,Indranil Chatterjee,Igor D. Jurberg,Eduardo C. Escudero-Adán,Paolo Melchiorre +5 more
TL;DR: Significant mechanistic insights are provided by the X-ray single-crystal analysis of an EDA complex relevant to the photoalkylation and the determination of the quantum yield of the process.
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Mechanism of the Stereoselective α-Alkylation of Aldehydes Driven by the Photochemical Activity of Enamines.
Ana Bahamonde,Paolo Melchiorre +1 more
TL;DR: The kinetic studies unveil the existence of a delicate interplay between the light-triggered initiation step and the radical chain propagation manifold, both mediated by the chiral enamines, as rate-determining in the enantioselective radical-trapping process.
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