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

PDF

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

Full Text

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

PDF
Album
1. Graphical Abstract
2. Scheme 1: Strategy for in situ generation of bromine.
  
  Jump to Scheme 1
3. Scheme 2: Synthesis of dibromophenol product 2b''.
  
  Jump to Scheme 2
4. Scheme 3: Scope of the photocatalytic bromination of alkenes.
  
  Jump to Scheme 3
5. Scheme 4: Bromination of diketones and cyclization reactions.
  
  Jump to Scheme 4
Supp. Info

Beilstein J. Org. Chem. 2014, 10, 622–627, doi:10.3762/bjoc.10.53

Full Text

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

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

Beilstein J. Org. Chem. 2014, 10, 863–876, doi:10.3762/bjoc.10.83

Full Text

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

PDF
Album
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...
  
  Jump to Scheme 1
3. Scheme 2: Ir-catalyzed formation of tricyclic product 10 by a domino radical addition reaction to α,β-unsatur...
  
  Jump to Scheme 2
4. Scheme 3: Ir-catalyzed addition reactions of N-methyl-N-((trimethylsilyl)methyl)aniline (5) to 5,6-dihydro-2H...
  
  Jump to Scheme 3
5. Scheme 4: Ir-catalyzed addition reactions of N-methyl-N-((trimethylsilyl)methyl)aniline (5) to 2-cyclopenteno...
  
  Jump to Scheme 4
6. Scheme 5: Ir-catalyzed formation of tricyclic products 19 by a domino radical addition reaction to α,β-unsatu...
  
  Jump to Scheme 5
7. Scheme 6: Ir-catalyzed addition reactions of N-methyl-N-((trimethylsilyl)methyl)aniline (5) to α,β-unsaturate...
  
  Jump to Scheme 6
8. Scheme 7: Ir-catalyzed addition reactions of N-methyl-N-((trimethylsilyl)methyl)aniline (5) to α,β-unsaturate...
  
  Jump to Scheme 7
9. Scheme 8: Cyclization of putative radical A to intermediate B competes with reduction of A to form addition p...
  
  Jump to Scheme 8
Supp. Info

Beilstein J. Org. Chem. 2014, 10, 890–896, doi:10.3762/bjoc.10.86

Full Text

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

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

Beilstein J. Org. Chem. 2014, 10, 936–947, doi:10.3762/bjoc.10.92

Full Text

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

PDF
Album
1. Graphical Abstract
2. Figure 1: Substrate scope.
  
  Jump to Figure 1
3. Scheme 1: Synthesis of a fused indoline.
  
  Jump to Scheme 1
4. Scheme 2: Proposed catalytic cycle.
  
  Jump to Scheme 2
Supp. Info

Beilstein J. Org. Chem. 2014, 10, 975–980, doi:10.3762/bjoc.10.96

Full Text

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

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

Beilstein J. Org. Chem. 2014, 10, 981–989, doi:10.3762/bjoc.10.97

Full Text

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

PDF
Album
1. Graphical Abstract
2. Scheme 1: Representative examples of multisubstituted CF₃-alkenes.
  
  Jump to Scheme 1
3. Scheme 2: Catalytic synthesis of CF₃-alkenes via trifluoromethylation.
  
  Jump to Scheme 2
4. Scheme 3: Our strategies for synthesis of CF₃-alkenes.
  
  Jump to Scheme 3
5. Scheme 4: Synthesis of geminal bis(trifluoromethyl)alkenes.
  
  Jump to Scheme 4
6. Scheme 5: A possible reaction mechanism.
  
  Jump to Scheme 5
7. Figure 1: Time profile of the photocatalytic trifluoromethylation of 2a with 1a with intermittent irradiation...
  
  Jump to Figure 1
Supp. Info

Beilstein J. Org. Chem. 2014, 10, 1099–1106, doi:10.3762/bjoc.10.108

Full Text

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

PDF
Album
1. Graphical Abstract
2. Scheme 1: Photohydroxymethylation of carbonyl compounds and imines.
  
  Jump to Scheme 1
3. Scheme 2: Model process: photocatalyzed acetophenone/methanol reaction.
  
  Jump to Scheme 2
4. Scheme 3: Photocatalyzed acetophenone/methanol reaction: types I–III.
  
  Jump to Scheme 3
5. Scheme 4: Photohydroxymethylation and subsequent lactonization of keto esters.
  
  Jump to Scheme 4
6. Scheme 5: Model reaction for heterogeneous and dye-sensitized catalysis.
  
  Jump to Scheme 5
7. Scheme 6: Product forming routes I to III for photoredox catalysis of methanol/carbonyl compounds.
  
  Jump to Scheme 6
8. Scheme 7: Photoredox initiated steps on semiconductor particle surfaces, CB, VB = conduction and valence band....
  
  Jump to Scheme 7
Supp. Info

Beilstein J. Org. Chem. 2014, 10, 1143–1150, doi:10.3762/bjoc.10.114

Full Text

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

PDF
Album
1. Graphical Abstract
2. Figure 1: Representative examples of lamellarin alkaloids.
  
  Jump to Figure 1
3. Scheme 1: Photocatalytic metal free construction of pyrrolo[2,1-a]isoquinolines.
  
  Jump to Scheme 1
4. Scheme 2: Evaluation of the substrate scope.
  
  Jump to Scheme 2
5. Scheme 3: Evaluation of the substrate scope with activated alkynes.
  
  Jump to Scheme 3
Supp. Info

Beilstein J. Org. Chem. 2014, 10, 1233–1238, doi:10.3762/bjoc.10.122

Full Text

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

Nathan J. Gesmundo and
David A. Nicewicz

Letter
Published 03 Jun 2014

PDF
Album
1. Graphical Abstract
2. Figure 1: Selected examples of endoperoxide-containing natural products.
  
  Jump to Figure 1
3. Scheme 1: Endoperoxide formation via cation radicals. In both examples, single electron oxidation is followed...
  
  Jump to Scheme 1
4. Scheme 2: Diversification strategy for endoperoxide synthesis by single electron transfer. E*_red vs SCE [20].
  
  Jump to Scheme 2
5. Figure 2: ORTEP of 3a.
  
  Jump to Figure 2
6. Scheme 3: Proposed mechanism for endoperoxide synthesis from tethered dienes.
  
  Jump to Scheme 3
7. Scheme 4: Competing formal [3,3] pathway.
  
  Jump to Scheme 4
Supp. Info

Beilstein J. Org. Chem. 2014, 10, 1272–1281, doi:10.3762/bjoc.10.128

Full Text

Visible light photoredox-catalyzed deoxygenation of alcohols

Daniel Rackl,
Viktor Kais,
Peter Kreitmeier and
Oliver Reiser

Full Research Paper
Published 10 Sep 2014

PDF
Album
1. Graphical Abstract
2. Scheme 1: Strategies for the visible light-catalysed deoxygenation of alcohols (reagents needed in (over-)sto...
  
  Jump to Scheme 1
3. Scheme 2: Reduction potentials of investigated derivatives 1–3 in DMF.
  
  Jump to Scheme 2
4. Scheme 3: Initial reaction conditions for deoxygenation candidates 1–3.
  
  Jump to Scheme 3
5. Scheme 4: Proposed reaction mechanism with and without additional water.
  
  Jump to Scheme 4
6. Scheme 5: Calculated spin densities of the radical anion and its protonated species.
  
  Jump to Scheme 5
7. Scheme 6: Synthesis of monobenzoate 6e.
  
  Jump to Scheme 6
8. Scheme 7: Reduction of benzoate moiety in case of non-benzylic alcohols.
  
  Jump to Scheme 7
9. Scheme 8: Optimized conditions for larger scale applications.
  
  Jump to Scheme 8
Supp. Info
Video

Beilstein J. Org. Chem. 2014, 10, 2157–2165, doi:10.3762/bjoc.10.223

Full Text

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

PDF
Album
1. Graphical Abstract
2. Scheme 1: Control experiment with liquid bromine for bromoethrification of alkenols.
  
  Jump to Scheme 1
3. Scheme 2: Proposed mechanism for the photocatalytic bromoetherification of alkenols.
  
  Jump to Scheme 2
Supp. Info

Beilstein J. Org. Chem. 2015, 11, 31–36, doi:10.3762/bjoc.11.5

Full Text

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

PDF
Album
1. Graphical Abstract
2. Scheme 1: Visible-light-induced sp³ C–H bond functionalization of tertiary amines.
  
  Jump to Scheme 1
3. Scheme 2: Substrate scope for aerobic oxidative cyclization of N,N-dimethylanilines with maleimides.
  
  Jump to Scheme 2
4. Scheme 3: A proposed reaction mechanism.
  
  Jump to Scheme 3
Supp. Info

Beilstein J. Org. Chem. 2015, 11, 425–430, doi:10.3762/bjoc.11.48

Full Text

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

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

Beilstein J. Org. Chem. 2015, 11, 568–575, doi:10.3762/bjoc.11.62

Full Text

Back to all Issues

Keep Informed

RSS Feed

Subscribe to our Latest Articles RSS Feed.

Subscribe

Email Notification

Register and get informed about new articles.

Register

Follow the Beilstein-Institut

Twitter: @BeilsteinInst