Efficient synthesis of 3,6,13,16-tetrasubstituted-tetrabenzo[a,d,j,m]coronenes by selective C–H/C–O arylations of anthraquinone derivatives

Seiya Terai,
Yuki Sato,
Takuya Kochi and
Fumitoshi Kakiuchi

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Published 31 Mar 2020

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1. Graphical Abstract
2. Scheme 1: Projected synthetic routes for 3,6,13,16-tetrasubstituted tetrabenzo[a,d,j,m]coronenes.
  
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3. Scheme 2: Reported syntheses of 2,7,12,17-tetrasubstituted tetrabenzo[a,d,j,m]coronenes.
  
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4. Scheme 3: C–H tetraarylation of anthraquinone (1).
  
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5. Scheme 4: C–H diarylation of 1,4-diarylanthraquinones 5.
  
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6. Figure 1: Normalized UV–vis absorption spectra of 7aa, 7bb, and 7ba.
  
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7. Figure 2: Effects of the concentration and the temperature on the ¹H NMR spectra of 7aa.
  
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Beilstein J. Org. Chem. 2020, 16, 544–550, doi:10.3762/bjoc.16.51

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Copper-catalyzed enantioselective conjugate reduction of α,β-unsaturated esters with chiral phenol–carbene ligands

Shohei Mimura,
Sho Mizushima,
Yohei Shimizu and
Masaya Sawamura

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Published 31 Mar 2020

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1. Graphical Abstract
2. Scheme 1: Proposed catalytic cycle.
  
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Beilstein J. Org. Chem. 2020, 16, 537–543, doi:10.3762/bjoc.16.50

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Copper-catalyzed remote C–H arylation of polycyclic aromatic hydrocarbons (PAHs)

Anping Luo,
Min Zhang,
Zhangyi Fu,
Jingbo Lan,
Di Wu and
Jingsong You

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Published 30 Mar 2020

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1. Graphical Abstract
2. Scheme 1: Direct C–H arylation of PAHs.
  
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3. Scheme 2: Scope of aryliodonium salts. Reaction conditions: 1a (0.2 mmol), 2 (0.3 mmol) in DCE (1 mL) at 70 °...
  
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4. Scheme 3: Scope of PAHs. Reaction conditions: 1 (0.2 mmol), 2a (0.3 mmol) in DCE (1 mL) at 70 °C under N₂ for...
  
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5. Scheme 4: Proposed catalytic cycle.
  
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6. Figure 1: a) UV-visible absorption spectra of 4k, 4n and 4o in toluene (1 × 10⁻⁵ mol/L). b) Emission spectra ...
  
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Beilstein J. Org. Chem. 2020, 16, 530–536, doi:10.3762/bjoc.16.49

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Synthesis of triphenylene-fused phosphole oxides via C–H functionalizations

Md. Shafiqur Rahman and
Naohiko Yoshikai

Letter
Published 27 Mar 2020

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1. Graphical Abstract
2. Figure 1: Examples of functional molecules based on π-extended phospholes.
  
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3. Scheme 1: Syntheses of PAH-fused phospholes featuring a 7-hydroxybenzo[b]phosphole as a key intermediate.
  
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4. Scheme 2: Synthesis of phosphole-fused ortho-teraryl compounds 7.
  
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5. Scheme 3: Oxidative cyclization of phosphole-fused ortho-teraryl compounds 7 into triphenylene-fused phosphol...
  
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6. Figure 2: ORTEP drawings of compound 8a (thermal ellipsoids set at 50% probability). a) top view; b) side vie...
  
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7. Figure 3: UV–vis absorption (solid lines) and fluorescence (dashed lines) spectra of compounds 8a–c.
  
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Beilstein J. Org. Chem. 2020, 16, 524–529, doi:10.3762/bjoc.16.48

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Regio- and stereoselective synthesis of new ensembles of diversely functionalized 1,3-thiaselenol-2-ylmethyl selenides by a double rearrangement reaction

Svetlana V. Amosova,
Andrey A. Filippov,
Nataliya A. Makhaeva,
Alexander I. Albanov and
Vladimir A. Potapov

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Published 27 Mar 2020

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1. Graphical Abstract
2. Scheme 1: Possible formation of reaction products starting from 1 via seleniranium 2 or thiiranium cations 3.
  
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3. Scheme 2: Unusual regio- and stereoselective nucleophilic reactions of thiaselenole 1 at two centers of the s...
  
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4. Scheme 3: Reactions of thiaselenole 1 with С- and S-centered nucleophiles affording new families of linear un...
  
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5. Scheme 4: The reactions of thiaselenole 1 with the formation of polyfunctionalized 2,3-dihydro-1,4-thiaseleni...
  
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6. Scheme 5: The synthesis of new 1,3-thiaselenole ensembles by reactions of thiaselenole 1 with mercapto benzaz...
  
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7. Scheme 6: The formation of product 4 via compound 5 by the reaction of thiaselenole 1 with potassium selenocy...
  
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8. Figure 1: Monitoring the reaction of thiaselenole 1 with KSeCN by ¹H NMR spectroscopy (in accordance with the...
  
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9. Scheme 7: The reaction pathway for the formation of compounds 4 and 5.
  
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10. Scheme 8: Synthesis of new ensembles of 1,3-thiaselenol-2-ylmethyl selenides 6a–l (⁷⁷Se NMR data are included...
  
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11. Scheme 9: The synthesis of vinyl selenides 7a,b through nucleophilic addition of 1,3-thiaselenol-2-ylmethylse...
  
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12. Scheme 10: One-pot synthesis of diselenide 8 from thiaselenole 1 (⁷⁷Se NMR data are included).
  
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13. Scheme 11: Synthesis of compounds 6a–j from diselenide 8.
  
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Beilstein J. Org. Chem. 2020, 16, 515–523, doi:10.3762/bjoc.16.47

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Exploring the scope of DBU-promoted amidations of 7-methoxycarbonylpterin

Anna R. Bockman and
Jeffrey M. Pruet

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Published 26 Mar 2020

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1. Graphical Abstract
2. Figure 1: The dual role of DBU in the amidation of 7-CMP.
  
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3. Scheme 1: DBU-promoted amidation of 7-CMP (1).
  
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4. Figure 2: Role of a β-hydroxy group in aiding the amidation reaction.
  
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5. Figure 3: Pseudo-first order kinetics for representative amines.
  
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Beilstein J. Org. Chem. 2020, 16, 509–514, doi:10.3762/bjoc.16.46

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Controlling alkyne reactivity by means of a copper-catalyzed radical reaction system for the synthesis of functionalized quaternary carbons

Goki Hirata,
Yu Yamane,
Naoya Tsubaki,
Reina Hara and
Takashi Nishikata

Letter
Published 26 Mar 2020

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1. Graphical Abstract
2. Scheme 1: Reaction modes of alkyne.
  
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3. Figure 1: Substrate scope of 1 and 2. ^aConducted at 80 °C for 24 h in MeCN with CuBr (10 mol %), 1,10-Phen (2...
  
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4. Scheme 2: Proposed mechanism.
  
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5. Scheme 3: Control experiment.
  
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6. Scheme 4: Reaction of 2a and 4a.
  
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7. Figure 2: Substrate scope of 2 and 4. ^aConducted at 100 °C for 20 h in 1,4-dioxane with CuI (10 mol %), 1,10-...
  
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Beilstein J. Org. Chem. 2020, 16, 502–508, doi:10.3762/bjoc.16.45

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KOt-Bu-promoted selective ring-opening N-alkylation of 2-oxazolines to access 2-aminoethyl acetates and N-substituted thiazolidinones

Qiao Lin,
Shiling Zhang and
Bin Li

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Published 25 Mar 2020

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1. Graphical Abstract
2. Scheme 1: Comparison of different ring-opening reactions of 2-oxazolines and thiazolidinones synthesis.
  
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3. Scheme 2: KOt-Bu-promoted selective ring-opening N-alkylation of 2-methyl-2-oxazoline with benzyl bromides. C...
  
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4. Scheme 3: KOt-Bu-promoted selective ring-opening N-alkylation of 2-methyl-2-oxazoline with benzyl chlorides. ...
  
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5. Scheme 4: KOt-Bu-promoted selective ring-opening N-alkylation of 2,4,4-trimethyl-4,5-dihydrooxazole (2b) with...
  
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6. Scheme 5: KOt-Bu/I₂-promoted selective N-alkylation to synthesis of thiazolidone derivatives. Conditions: KOt...
  
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7. Scheme 6: Transformation of 2-aminoethyl acetate derivative to 2-(dibenzylamino)ethanol.
  
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8. Scheme 7: Control experiments and ¹⁸O-labeling experiment.
  
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9. Scheme 8: Control experiments with radical scavengers.
  
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10. Scheme 9: Proposed mechanism.
  
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Beilstein J. Org. Chem. 2020, 16, 492–501, doi:10.3762/bjoc.16.44

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Aerobic synthesis of N-sulfonylamidines mediated by N-heterocyclic carbene copper(I) catalysts

Faïma Lazreg,
Marie Vasseur,
Alexandra M. Z. Slawin and
Catherine S. J. Cazin

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Published 24 Mar 2020

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1. Graphical Abstract
2. Scheme 1: Formation of sulfonyltriazoles and sulfonamidines.
  
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3. Figure 1: Catalytic systems used in this study.
  
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4. Scheme 2: Synthetic access to complexes 4–6 [30].
  
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5. Scheme 3: Variation of sulfonylazides. Reaction conditions: phenylacetylene (0.5 mmol), sulfonyl azide (0.6 m...
  
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6. Scheme 4: Variation of alkynes. Reaction conditions: alkyne (0.5 mmol), tosyl azide (0.6 mmol), diisopropylam...
  
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7. Scheme 5: Variation of the amine substrate. Reaction conditions: phenylacetylene (0.5 mmol), tosyl azide (0.6...
  
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8. Scheme 6: Reactivity of “non-sulfonyl” azide [33]. Reaction conditions: phenylacetylene (0.5 mmol), benzyl azide ...
  
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9. Scheme 7: Reactivity of diphenylphosphoryl azide. Reaction conditions: phenylacetylene (0.5 mmol), diphenylph...
  
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10. Scheme 8: Proposed mechanism for the formation of sulfonamidine.
  
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11. Scheme 9: Stoichiometric reaction between 6 and 8.
  
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12. Scheme 10: Synthesis of copper-acetylide intermediate A via [Cu(Cl)(Triaz)].
  
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13. Scheme 11: Catalytic reaction involving copper-acetylide complex A.
  
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Beilstein J. Org. Chem. 2020, 16, 482–491, doi:10.3762/bjoc.16.43

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Recent advances in photocatalyzed reactions using well-defined copper(I) complexes

Mingbing Zhong,
Xavier Pannecoucke,
Philippe Jubault and
Thomas Poisson

Review
Published 23 Mar 2020

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1. Graphical Abstract
2. Scheme 1: [Cu(I)(dap)₂]Cl-catalyzed ATRA reaction under green light irradiation.
  
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3. Scheme 2: Photocatalytic allylation of α-haloketones.
  
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4. Scheme 3: [Cu(I)(dap)₂]Cl-photocatalyzed chlorosulfonylation and chlorotrifluoromethylation of alkenes.
  
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5. Scheme 4: Photocatalytic perfluoroalkylchlorination of electron-deficient alkenes using the Sauvage catalyst.
  
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6. Scheme 5: Photocatalytic synthesis of fluorinated sultones.
  
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7. Scheme 6: Photocatalyzed haloperfluoroalkylation of alkenes and alkynes.
  
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8. Scheme 7: Chlorosulfonylation of alkenes catalyzed by [Cu(I)(dap)₂]Cl. ^aNo Na₂CO₃ was added. ^b1 equiv of Na₂CO...
  
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9. Scheme 8: Copper-photocatalyzed reductive allylation of diaryliodonium salts.
  
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10. Scheme 9: Copper-photocatalyzed azidomethoxylation of olefins.
  
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11. Scheme 10: Benzylic azidation initiated by [Cu(I)(dap)₂]Cl.
  
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12. Scheme 11: Trifluoromethyl methoxylation of styryl derivatives using [Cu(I)(dap)₂]PF₆. All redox potentials ar...
  
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13. Scheme 12: Trifluoromethylation of silyl enol ethers.
  
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14. Scheme 13: Synthesis of annulated heterocycles upon oxidation with the Sauvage catalyst.
  
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15. Scheme 14: Oxoazidation of styrene derivatives using [Cu(dap)₂]Cl as a precatalyst.
  
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16. Scheme 15: [Cu(I)(dpp)(binc)]PF₆-catalyzed ATRA reaction.
  
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17. Scheme 16: Allylation reaction of α-bromomalonate catalyzed by [Cu(I)(dpp)(binc)]PF₆ following an ATRA mechani...
  
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18. Scheme 17: Bromo/tribromomethylation reaction using [Cu(I)(dmp)(BINAP)]PF₆.
  
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19. Scheme 18: Chlorotrifluoromethylation of alkenes catalyzed by [Cu(I)(N^N)(xantphos)]PF₆.
  
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20. Scheme 19: Chlorosulfonylation of styrene and alkyne derivatives by ATRA reactions.
  
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21. Scheme 20: Reduction of aryl and alkyl halides with the complex [Cu(I)(bcp)(DPEPhos)]PF₆. ^aIrradiation was car...
  
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22. Scheme 21: Meerwein arylation of electron-rich aromatic derivatives and 5-exo-trig cyclization catalyzed by th...
  
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23. Scheme 22: [Cu(I)(bcp)(DPEPhos)]PF₆-photocatalyzed synthesis of alkaloids. ^aYield over two steps (cyclization ...
  
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24. Scheme 23: Copper-photocatalyzed decarboxylative amination of NHP esters.
  
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25. Scheme 24: Photocatalytic decarboxylative alkynylation using [Cu(I)(dq)(binap)]BF₄.
  
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26. Scheme 25: Copper-photocatalyzed alkylation of glycine esters.
  
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27. Scheme 26: Copper-photocatalyzed borylation of organic halides. ^aUnder continuous flow conditions.
  
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28. Scheme 27: Copper-photocatalyzed α-functionalization of alcohols with glycine ester derivatives.
  
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29. Scheme 28: δ-Functionalization of alcohols using [Cu(I)(dmp)(xantphos)]BF₄.
  
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30. Scheme 29: Photocatalytic synthesis of [5]helicene and phenanthrene.
  
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31. Scheme 30: Oxidative carbazole synthesis using in situ-formed [Cu(I)(dmp)(xantphos)]BF₄.
  
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32. Scheme 31: Copper-photocatalyzed functionalization of N-aryl tetrahydroisoquinolines.
  
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33. Scheme 32: Bicyclic lactone synthesis using a copper-photocatalyzed PCET reaction.
  
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34. Scheme 33: Photocatalytic Pinacol coupling reaction catalyzed by [Cu(I)(pypzs)(BINAP)]BF₄. The ligands of the ...
  
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35. Scheme 34: Azide photosensitization using a Cu-based photocatalyst.
  
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Beilstein J. Org. Chem. 2020, 16, 451–481, doi:10.3762/bjoc.16.42

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