Organic synthesis using photoredox catalysis

Editor: Prof. Axel G. Griesbeck
Universität zu Köln

Natural photosynthesis is a remarkable chemical machinery that enables our life on earth and delivers a constant stream of oxygen and organic biomass. We should acknowledge this fact with humbleness, especially because we have not been able yet to mimic this process in a reliable way even after decades of intense research. The basic mechanistic principle behind photosynthesis is photoredox catalysis or light-driven charge separation, which leads to an energy harvesting process by taking advantage of the reduction products and filling the holes by a sacrificial electron donor, water. In contrast to the “traditional” catalysis areas such as metal-, organo- and biocatalysis, photoredox catalysis (and photocatalysis in general) is a young research field with regard to synthetic applications. The collection of papers in this Thematic Series on organic synthesis using photoredox catalysis shows this convincingly.

See also the Thematic Series:
Photocycloadditions and photorearrangements

Organic synthesis using photoredox catalysis

Axel G. Griesbeck

Editorial
Published 12 May 2014

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Beilstein J. Org. Chem. 2014, 10, 1097–1098, doi:10.3762/bjoc.10.107

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Visible-light photoredox catalysis enabled bromination of phenols and alkenes

Yating Zhao,
Zhe Li,
Chao Yang,
Run Lin and
Wujiong Xia

Full Research Paper
Published 07 Mar 2014

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1. Graphical Abstract
2. Scheme 1: Strategy for in situ generation of bromine.
  
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3. Scheme 2: Synthesis of dibromophenol product 2b''.
  
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4. Scheme 3: Scope of the photocatalytic bromination of alkenes.
  
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5. Scheme 4: Bromination of diketones and cyclization reactions.
  
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Beilstein J. Org. Chem. 2014, 10, 622–627, doi:10.3762/bjoc.10.53

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Metal and metal-free photocatalysts: mechanistic approach and application as photoinitiators of photopolymerization

Jacques Lalevée,
Sofia Telitel,
Pu Xiao,
Marc Lepeltier,
Frédéric Dumur,
Fabrice Morlet-Savary,
Didier Gigmes and
Jean-Pierre Fouassier

Full Research Paper
Published 15 Apr 2014

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1. Graphical Abstract
2. Scheme 1: Examples of photoinitiating systems.
  
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3. Figure 1: Previously reported PIC (based on metal complexes) [45-52].
  
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4. Figure 2: Previously reported PIC (metal free organic molecules) [54,55].
  
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5. Scheme 2: Reaction mechanisms for the three-component system PIC/eA/E-Z.
  
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6. Scheme 3: Reaction mechanisms for the two-component system PIC/eA.
  
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7. Scheme 4: Reaction mechanisms for the system PIC/eA/add.
  
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8. Scheme 5: Reaction mechanisms for the system PIC/eD/B-Y.
  
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9. Figure 3: Typical oxidation and reduction agents used through the photoredox catalysis approach in polymeriza...
  
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10. Figure 4: Typical monomers that can be polymerized through a photoredox catalysis approach.
  
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11. Scheme 6: Reaction mechanisms for the system Ru(bpy)₃²⁺/Ph₂I⁺/R₃SiH.
  
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12. Scheme 7: Reaction mechanisms for the Ru(ligand)₃²⁺/Ph₃S⁺/R₃SiH system.
  
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13. Scheme 8: Reaction mechanisms for the Ru(ligand)₃²⁺/Ph₂I⁺/NVK system upon visible lights.
  
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14. Scheme 9: Reaction mechanisms for the violanthrone/Ph₂I⁺/TTMSS (R₃SiH) system upon red lights.
  
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15. Scheme 10: Reaction mechanisms for the Tr-AD/R-Br/MDEA system upon visible lights.
  
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16. Scheme 11: The photoredox catalysis for controlled polymerization reactions.
  
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17. Scheme 12: Reaction mechanisms for the Ru(ligand)₃²⁺/MDEA/R-Br system upon visible lights.
  
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18. Scheme 13: Reaction mechanisms for the Violanthrone/Ru(ligand)₃²⁺/Ph₂I⁺/R₃SiH system upon visible lights.
  
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19. Scheme 14: Reaction mechanisms for the MK/amine/triazine system upon visible lights.
  
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20. Figure 5: The new proposed PIC (Ir(piq)₂(tmd)).
  
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21. Figure 6: UV–visible light absorption spectra for Ir(piq)₂(tmd) (2) and Ir(ppy)₃ (1); solvent: acetonitrile.
  
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22. Figure 7: (A) cyclic voltamogramm for Ir(piq)₂(tmd) in acetonitrile; (B) absorption (a) and luminescence (b) ...
  
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23. Figure 8: Photolysis of a Ir(piq)₂(tmd)/Ph₂I⁺ solution ([Ph₂I⁺] = 0.023 M, in acetonitrile) upon a halogen la...
  
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24. Figure 9: ESR spin-trapping spectra for the irradiation of a Ir(piq)₂(tmd)/Ph₂I⁺ solution in the presence of ...
  
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25. Figure 10: (A) Photopolymerization profile of EPOX; photoinitiating system: Ir(piq)₂(tmd)/Ph₂I⁺/NVK (1%/2%/3%)...
  
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26. Figure 11: (A) Photopolymerization profile of TMPTA; initiating systems: (1) Ir(piq)₂(tmd)/MDEA (1%/2%) and (2...
  
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Beilstein J. Org. Chem. 2014, 10, 863–876, doi:10.3762/bjoc.10.83

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Visible-light-induced, Ir-catalyzed reactions of N-methyl-N-((trimethylsilyl)methyl)aniline with cyclic α,β-unsaturated carbonyl compounds

Dominik Lenhart and
Thorsten Bach

Full Research Paper
Published 17 Apr 2014

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1. Graphical Abstract
2. Scheme 1: PET-catalyzed addition of N,N-dimethylaniline (1) to furan-2(5H)-one 2 [38] and of N-methyl-N-((trimeth...
  
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3. Scheme 2: Ir-catalyzed formation of tricyclic product 10 by a domino radical addition reaction to α,β-unsatur...
  
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4. Scheme 3: Ir-catalyzed addition reactions of N-methyl-N-((trimethylsilyl)methyl)aniline (5) to 5,6-dihydro-2H...
  
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5. Scheme 4: Ir-catalyzed addition reactions of N-methyl-N-((trimethylsilyl)methyl)aniline (5) to 2-cyclopenteno...
  
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6. Scheme 5: Ir-catalyzed formation of tricyclic products 19 by a domino radical addition reaction to α,β-unsatu...
  
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7. Scheme 6: Ir-catalyzed addition reactions of N-methyl-N-((trimethylsilyl)methyl)aniline (5) to α,β-unsaturate...
  
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8. Scheme 7: Ir-catalyzed addition reactions of N-methyl-N-((trimethylsilyl)methyl)aniline (5) to α,β-unsaturate...
  
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9. Scheme 8: Cyclization of putative radical A to intermediate B competes with reduction of A to form addition p...
  
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Beilstein J. Org. Chem. 2014, 10, 890–896, doi:10.3762/bjoc.10.86

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Tailoring of organic dyes with oxidoreductive compounds to obtain photocyclic radical generator systems exhibiting photocatalytic behavior

Christian Ley,
Julien Christmann,
Ahmad Ibrahim,
Luciano H. Di Stefano and
Xavier Allonas

Full Research Paper
Published 25 Apr 2014

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1. Graphical Abstract
2. Scheme 1: Chemical structures of RB, EDB and TA.
  
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3. Scheme 2: Type II PIS mechanisms. PS: photosensitizer; ^1,3PS^*: singlet and triplet PS excited states; PS^•+: o...
  
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4. Figure 1: Evolution of RB concentration as a function of irradiation time (λ = 532 nm, 9 mW·cm⁻³); insert: ab...
  
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5. Scheme 3: Photocatalytic behavior occurring in three component PIS. PS: photosensitizer; ^1,3PS^*: singlet and ...
  
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6. Figure 2: Evolution of [RB](t) in the photocyclic system RB/TA/EDB as a function of irradiation time (λ = 532...
  
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7. Scheme 4: Thermodynamics of an oxidative three components PCIS, a) ground state reaction (), b) excited state...
  
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8. Scheme 5: General photocatalytic cycle occurring in three components photocyclic systems. Two cycles are in c...
  
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9. Figure 3: Mechanistic description of photocyclic system involved in the RB/TA/EDB system. The rate constants ...
  
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10. Figure 4: Evolution of RB, RB^•+, TA, and TA^•− concentration with time for RB/TA system.
  
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11. Figure 5: Evolution of RB, TA and EDB concentrations in the photocyclic system. The logarithm of oxidative an...
  
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12. Figure 6: Evolution of radical concentrations TA^•− and EDB^•+ together with [RB] in photocatalytic system.
  
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Beilstein J. Org. Chem. 2014, 10, 936–947, doi:10.3762/bjoc.10.92

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Visible light mediated intermolecular [3 + 2] annulation of cyclopropylanilines with alkynes

Theresa H. Nguyen,
Soumitra Maity and
Nan Zheng

Full Research Paper
Published 29 Apr 2014

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1. Graphical Abstract
2. Figure 1: Substrate scope.
  
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3. Scheme 1: Synthesis of a fused indoline.
  
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4. Scheme 2: Proposed catalytic cycle.
  
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Beilstein J. Org. Chem. 2014, 10, 975–980, doi:10.3762/bjoc.10.96

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On the mechanism of photocatalytic reactions with eosin Y

Michal Majek,
Fabiana Filace and
Axel Jacobi von Wangelin

Full Research Paper
Published 30 Apr 2014

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1. Graphical Abstract
2. Scheme 1: Oxidative quenching of eosin Y with arenediazonium salts and reactions of the resultant aryl radica...
  
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3. Scheme 2: Proposed general reaction mechanism of eosin Y-catalyzed substitutions with arene diazonium salts.
  
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4. Figure 1: UV–vis spectra of the photoborylation reaction mixture (RM).
  
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5. Figure 2: Fluorescence spectra of the photoborylation reaction mixture (RM). Ex. = excitation wavelength.
  
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6. Scheme 3: Acid–base behaviour of eosin Y.
  
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7. Figure 3: UV–vis spectrum of p-bromobenzenediazonium tetrafluoroborate (pBrPhN₂) and bispinacolato diboron (B₂...
  
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8. Scheme 4: Eosin Y-catalyzed and dye-free photolytic borylation.
  
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9. Scheme 5: Eosin Y-catalyzed and dye-free reactions with ethyl propiolate.
  
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10. Figure 4: UV–vis spectra of ortho-biphenyldiazonium tetrafluoroborate (biPhN₂) in acetonitrile.
  
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11. Scheme 6: Quantum yield determinations of selected visible-light-driven aromatic substitutions.
  
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Beilstein J. Org. Chem. 2014, 10, 981–989, doi:10.3762/bjoc.10.97

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Direct C–H trifluoromethylation of di- and trisubstituted alkenes by photoredox catalysis

Ren Tomita,
Yusuke Yasu,
Takashi Koike and
Munetaka Akita

Full Research Paper
Published 12 May 2014

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1. Graphical Abstract
2. Scheme 1: Representative examples of multisubstituted CF₃-alkenes.
  
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3. Scheme 2: Catalytic synthesis of CF₃-alkenes via trifluoromethylation.
  
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4. Scheme 3: Our strategies for synthesis of CF₃-alkenes.
  
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5. Scheme 4: Synthesis of geminal bis(trifluoromethyl)alkenes.
  
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6. Scheme 5: A possible reaction mechanism.
  
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7. Figure 1: Time profile of the photocatalytic trifluoromethylation of 2a with 1a with intermittent irradiation...
  
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Beilstein J. Org. Chem. 2014, 10, 1099–1106, doi:10.3762/bjoc.10.108

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Homogeneous and heterogeneous photoredox-catalyzed hydroxymethylation of ketones and keto esters: catalyst screening, chemoselectivity and dilution effects

Axel G. Griesbeck and
Melissa Reckenthäler

Full Research Paper
Published 19 May 2014

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1. Graphical Abstract
2. Scheme 1: Photohydroxymethylation of carbonyl compounds and imines.
  
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3. Scheme 2: Model process: photocatalyzed acetophenone/methanol reaction.
  
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4. Scheme 3: Photocatalyzed acetophenone/methanol reaction: types I–III.
  
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5. Scheme 4: Photohydroxymethylation and subsequent lactonization of keto esters.
  
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6. Scheme 5: Model reaction for heterogeneous and dye-sensitized catalysis.
  
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7. Scheme 6: Product forming routes I to III for photoredox catalysis of methanol/carbonyl compounds.
  
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8. Scheme 7: Photoredox initiated steps on semiconductor particle surfaces, CB, VB = conduction and valence band....
  
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Beilstein J. Org. Chem. 2014, 10, 1143–1150, doi:10.3762/bjoc.10.114

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Visible-light photoredox catalyzed synthesis of pyrroloisoquinolines via organocatalytic oxidation/[3 + 2] cycloaddition/oxidative aromatization reaction cascade with Rose Bengal

Carlos Vila,
Jonathan Lau and
Magnus Rueping

Letter
Published 27 May 2014

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1. Graphical Abstract
2. Figure 1: Representative examples of lamellarin alkaloids.
  
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3. Scheme 1: Photocatalytic metal free construction of pyrrolo[2,1-a]isoquinolines.
  
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4. Scheme 2: Evaluation of the substrate scope.
  
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5. Scheme 3: Evaluation of the substrate scope with activated alkynes.
  
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Beilstein J. Org. Chem. 2014, 10, 1233–1238, doi:10.3762/bjoc.10.122

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Cyclization–endoperoxidation cascade reactions of dienes mediated by a pyrylium photoredox catalyst

Nathan J. Gesmundo and
David A. Nicewicz

Letter
Published 03 Jun 2014

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1. Graphical Abstract
2. Figure 1: Selected examples of endoperoxide-containing natural products.
  
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3. Scheme 1: Endoperoxide formation via cation radicals. In both examples, single electron oxidation is followed...
  
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4. Scheme 2: Diversification strategy for endoperoxide synthesis by single electron transfer. E*_red vs SCE [20].
  
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5. Figure 2: ORTEP of 3a.
  
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6. Scheme 3: Proposed mechanism for endoperoxide synthesis from tethered dienes.
  
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7. Scheme 4: Competing formal [3,3] pathway.
  
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Beilstein J. Org. Chem. 2014, 10, 1272–1281, doi:10.3762/bjoc.10.128

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Visible light photoredox-catalyzed deoxygenation of alcohols

Daniel Rackl,
Viktor Kais,
Peter Kreitmeier and
Oliver Reiser

Full Research Paper
Published 10 Sep 2014

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1. Graphical Abstract
2. Scheme 1: Strategies for the visible light-catalysed deoxygenation of alcohols (reagents needed in (over-)sto...
  
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3. Scheme 2: Reduction potentials of investigated derivatives 1–3 in DMF.
  
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4. Scheme 3: Initial reaction conditions for deoxygenation candidates 1–3.
  
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5. Scheme 4: Proposed reaction mechanism with and without additional water.
  
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6. Scheme 5: Calculated spin densities of the radical anion and its protonated species.
  
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7. Scheme 6: Synthesis of monobenzoate 6e.
  
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8. Scheme 7: Reduction of benzoate moiety in case of non-benzylic alcohols.
  
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9. Scheme 8: Optimized conditions for larger scale applications.
  
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Beilstein J. Org. Chem. 2014, 10, 2157–2165, doi:10.3762/bjoc.10.223

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Visible-light-induced bromoetherification of alkenols for the synthesis of β-bromotetrahydrofurans and -tetrahydropyrans

Run Lin,
Hongnan Sun,
Chao Yang,
Youdong Yang,
Xinxin Zhao and
Wujiong Xia

Full Research Paper
Published 08 Jan 2015

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1. Graphical Abstract
2. Scheme 1: Control experiment with liquid bromine for bromoethrification of alkenols.
  
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3. Scheme 2: Proposed mechanism for the photocatalytic bromoetherification of alkenols.
  
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Beilstein J. Org. Chem. 2015, 11, 31–36, doi:10.3762/bjoc.11.5

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Eosin Y-catalyzed visible-light-mediated aerobic oxidative cyclization of N,N-dimethylanilines with maleimides

Zhongwei Liang,
Song Xu,
Wenyan Tian and
Ronghua Zhang

Full Research Paper
Published 01 Apr 2015

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1. Graphical Abstract
2. Scheme 1: Visible-light-induced sp³ C–H bond functionalization of tertiary amines.
  
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3. Scheme 2: Substrate scope for aerobic oxidative cyclization of N,N-dimethylanilines with maleimides.
  
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4. Scheme 3: A proposed reaction mechanism.
  
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Beilstein J. Org. Chem. 2015, 11, 425–430, doi:10.3762/bjoc.11.48

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Photocatalytic nucleophilic addition of alcohols to styrenes in Markovnikov and anti-Markovnikov orientation

Martin Weiser,
Sergej Hermann,
Alexander Penner and
Hans-Achim Wagenknecht

Full Research Paper
Published 27 Apr 2015

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1. Graphical Abstract
2. Scheme 1: Photooxidation of the substrate and reductive quenching of the photocatalyst (left) vs photoreducti...
  
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3. Scheme 2: Mechanism of the Markovnikov-type photocatalytic addition of methanol to 1,1-diphenylethylene (1) a...
  
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4. Scheme 3: Intramolecular photocatalytic addition with substrate 3; reaction conditions: 3 (2 mM), Py (2 mM), ...
  
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5. Scheme 4: Proposed mechanism of the anti-Markovnikov-type photocatalytic addition of methanol to 1,1-diphenyl...
  
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6. Figure 1: Conversion of substrate 1 and formation of product 5 observed during photocatalysis with PDI in the...
  
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7. Figure 2: Conversion of substrate 1 (black dashed) and formation of product 5 (red solid) observed during pho...
  
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8. Figure 3: Spectra of PDI before (dotted black) and after excitation (red), then every 2 min until ground stat...
  
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9. Scheme 5: Intramolecular additions of substrates 8 and 10 to demonstrate the effect of different electron den...
  
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Beilstein J. Org. Chem. 2015, 11, 568–575, doi:10.3762/bjoc.11.62

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