Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)
Published: May 7, 2024
Herein, we develop a straightforward, metal-free, and acid-/base-free electrochemical C4-selective C - H deuteration of pyridine derivatives with economic convenient D
Language: Английский
Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(8), P. 4237 - 4352
Published: Jan. 24, 2023
The emergence of modern photocatalysis, characterized by mildness and selectivity, has significantly spurred innovative late-stage C–H functionalization approaches that make use low energy photons as a controllable source. Compared to traditional strategies, photocatalysis paves the way toward complementary and/or previously unattainable regio- chemoselectivities. Merging compelling benefits with workflow offers potentially unmatched arsenal tackle drug development campaigns beyond. This Review highlights photocatalytic strategies small-molecule drugs, agrochemicals, natural products, classified according targeted bond newly formed one. Emphasis is devoted identifying, describing, comparing main mechanistic scenarios. draws critical comparison between established ionic chemistry photocatalyzed radical-based manifolds. aims establish current state-of-the-art illustrate key unsolved challenges be addressed in future. authors aim introduce general readership functionalization, specialist practitioners evaluation methodologies, potential for improvement, future uncharted directions.
Language: Английский
Citations
322
Nature Reviews Drug Discovery, Journal Year: 2023, Volume and Issue: 22(7), P. 562 - 584
Published: June 5, 2023
Language: Английский
Citations
243
Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)
Published: June 30, 2022
Abstract Herein, a facile and general electroreductive deuteration of unactivated alkyl halides (X = Cl, Br, I) or pseudo-halides OMs) using D 2 O as the economical deuterium source was reported. In addition to primary secondary halides, sterically hindered tertiary chlorides also work very well, affording target deuterodehalogenated products with excellent efficiency incorporation. More than 60 examples are provided, including late-stage dehalogenative natural products, pharmaceuticals, their derivatives, all incorporation (up 99% D), demonstrating potential utility developed method in organic synthesis. Furthermore, does not require external catalysts tolerates high current, showing possible use industrial applications.
Language: Английский
Citations
106
Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(41)
Published: May 15, 2023
Catalytic hydrogen atom transfer from metal-hydrides to alkenes allows feedstock olefins be used as alkyl radical precursors. The chemoselectivity of this process makes it an attractive synthetic tool and such has been regularly in synthesis complex molecules. However, onwards reactivity is limited by compatibility with the conditions which form key metal-hydride species. Now, through merger photocatalysis or electrochemistry, milder methods are emerging can unlock entirely new offer perspectives on expanding these unprecedented directions. This review outlines most recent developments electro- photochemical cobalt catalysed offers suggestions future outlook.
Language: Английский
Citations
57
Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(45)
Published: Sept. 12, 2023
Despite widespread use of the deuterium isotope effect, selective labeling chemical molecules remains a major challenge. Herein, facile and general electrochemically driven, organic mediator enabled deuteration styrenes with oxide (D2 O) as economical source was reported. Importantly, this transformation could be suitable for various electron rich mediated by triphenylphosphine (TPP). The reaction proceeded under mild conditions without transition-metal catalysts, affording desired products in good yields excellent D-incorporation (D-inc, up to >99 %). Mechanistic investigations means experiments cyclic voltammetry tests provided sufficient support transformation. Notably, method proved powerful tool late-stage biorelevant compounds.
Language: Английский
Citations
48
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(2), P. 1410 - 1422
Published: Jan. 5, 2024
Alkene radical ions constitute an integral and unique class of reactive intermediates for the synthesis valuable compounds because they have both unpaired spins charge. However, relatively few synthetic applications alkene anions emerged due to a dearth generally applicable mild anion generation approaches. Precise control over chemo- stereoselectivity in anion-mediated processes represents another long-standing challenge their high reactivity. To overcome these issues, here, we develop new redox-neutral strategy that seamlessly merges photoredox copper catalysis enable controlled orthogonal enantioselective cyanofunctionalization via distonic-like species. This enables highly regio-, chemo-, hydrocyanation, deuterocyanation, cyanocarboxylation alkenes without stoichiometric reductants or oxidants under visible light irradiation. protocol provides blueprint exploration transformation potential anions.
Language: Английский
Citations
39
ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(3), P. 1300 - 1310
Published: Jan. 11, 2024
Directly utilizing abundant and inexpensive sources of aliphatic carboxylic acids is highly attractive for the synthesis CF2H- CH3-containing compounds. Herein, we report a versatile photoinduced iron-catalyzed platform hydrodifluoromethylation hydromethylation alkenes without need additional stoichiometric oxidants. These two transformations are accomplished by visible-light-induced ligand-to-iron charge transfer open-shell activation system using industrial chemical difluoroacetic acetic as precursors postulated to operate via difluoromethyl methyl radical-mediated decarboxylation mechanism. Experimental results show that strategy also applicable difunctionalization unactivated alkenes. Meanwhile, this provides viable route pharmaceutically active molecules containing deuterated units. The protocol exhibits several features, including mild reaction conditions, divergent radical precursors, operational simplicity scalability, good chemo- regioselectivity, scalability supported continuous flow technology, ability provide high-value building blocks applications in one step.
Language: Английский
Citations
37
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(2), P. 1250 - 1256
Published: Jan. 8, 2024
Luminescent covalent organic frameworks (LCOFs) have emerged as indispensable candidates in various applications due to their greater tunable emitting properties and structural robustness compared small molecule emitters. An unsolved issue this area is developing highly luminescent LCOFs of which the nonradiative quenching pathways were suppressed much possible. Here, a robust aminal-linked COF (DD-COF) possessing perdeuterated light-emitting monomers was designed synthesized. The solid-state photoluminescence quantum yield DD-COF reaches 81%, significantly outcompeting all state-of-the-art reported so far. exceptional efficiency attributed inhibition different decay, especially from bond vibrations where only substitution by heavier isotope with lower zero-point vibration frequency works. Furthermore, prepared deuterated not boosts higher photostability under UV irradiation but also enables superior fluorescence sensing performance for iodine detection nondeuterated COF.
Language: Английский
Citations
18
Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown
Published: Feb. 4, 2025
Traditional reductions of alkenes, such as using stoichiometric reductants with waste generation and catalytic hydrogenation high-pressure H2, are accompanied by environmental or safety issues. Herein, we demonstrated a universal method for the electrocatalytic deuteration alkenes modified electrodes under ambient temperature. The key M-H/M-D species alkene reduction were generated from electrolysis H2O/D2O on electrodes, which avoided usage H2 D2. Mono-, di-, tri-, tetra-substituted successfully reduced in this system H2O D2O hydrogen deuterium sources. Electron-donating/-withdrawing other easily reducible functional groups, complicated natural products drugs all reductive hydrogenated deuterated excellent yields (85 examples, up to 99%). Faraday efficiency efficient could reach 84%. Moreover, amount metal decrease less than 0.01 mol %.
Language: Английский
Citations
2
Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)
Published: Aug. 1, 2022
Abstract Site- and enantioselective incorporation of deuterium into organic compounds is broad interest in synthesis, especially within the pharmaceutical industry. While catalytic approaches relying on two-electron reaction manifolds have allowed for stereoselective delivery a formal deuteride (D – ) or deuteron + at benzylic positions, complementary strategies that make use one-electron atom transfer target non-benzylic positions remain elusive. Here we report photochemical approach asymmetric radical deuteration by utilizing readily available peptide- sugar-derived thiols as catalyst inexpensive oxide source. This metal-free platform enables four types deuterofunctionalization reactions exocyclic olefins allows with high levels enantioselectivity incorporation. Computational studies reveal attractive non-covalent interactions are responsible stereocontrol. We anticipate our findings will open up new avenues deuteration.
Language: Английский
Citations
68