Dichloromethylation of enones by carbon nitride photocatalysis.
Journal
Nature communications
ISSN: 2041-1723
Titre abrégé: Nat Commun
Pays: England
ID NLM: 101528555
Informations de publication
Date de publication:
13 Mar 2020
13 Mar 2020
Historique:
received:
09
08
2019
accepted:
13
02
2020
entrez:
15
3
2020
pubmed:
15
3
2020
medline:
15
3
2020
Statut:
epublish
Résumé
Small organic radicals are ubiquitous intermediates in photocatalysis and are used in organic synthesis to install functional groups and to tune electronic properties and pharmacokinetic parameters of the final molecule. Development of new methods to generate small organic radicals with added functionality can further extend the utility of photocatalysis for synthetic needs. Herein, we present a method to generate dichloromethyl radicals from chloroform using a heterogeneous potassium poly(heptazine imide) (K-PHI) photocatalyst under visible light irradiation for C1-extension of the enone backbone. The method is applied on 15 enones, with γ,γ-dichloroketones yields of 18-89%. Due to negative zeta-potential (-40 mV) and small particle size (100 nm) K-PHI suspension is used in quasi-homogeneous flow-photoreactor increasing the productivity by 19 times compared to the batch approach. The resulting γ,γ-dichloroketones, are used as bifunctional building blocks to access value-added organic compounds such as substituted furans and pyrroles.
Identifiants
pubmed: 32170119
doi: 10.1038/s41467-020-15131-0
pii: 10.1038/s41467-020-15131-0
pmc: PMC7070069
doi:
Types de publication
Journal Article
Langues
eng
Sous-ensembles de citation
IM
Pagination
1387Subventions
Organisme : Deutsche Forschungsgemeinschaft (German Research Foundation)
ID : DFG-An 156 13-1
Références
Ghosh, I. et al. Organic semiconductor photocatalyst can bifunctionalize arenes and heteroarenes. Science 365, 360–366 (2019).
pubmed: 31346061
doi: 10.1126/science.aaw3254
Pieber, B., Shalom, M., Antonietti, M., Seeberger, P. H. & Gilmore, K. Continuous heterogeneous photocatalysis in serial micro-batch reactors. Angew. Chem. Int. Ed. 57, 9976–9979 (2018).
doi: 10.1002/anie.201712568
Kurpil, B., Otte, K., Antonietti, M. & Savateev, A. Photooxidation of N-acylhydrazones to 1,3,4-oxadiazoles catalyzed by heterogeneous visible-light-active carbon nitride semiconductor. Appl. Catal. B 228, 97–102 (2018).
doi: 10.1016/j.apcatb.2018.01.072
Savateev, A., Ghosh, I., König, B. & Antonietti, M. Photoredox catalytic organic transformations using heterogeneous carbon nitrides. Angew. Chem. Int. Ed. 57, 15936–15947 (2018).
Markushyna, Y., Smith, C. A. & Savateev, A. Organic photocatalysis: carbon nitride semiconductors vs. molecular catalysts. Eur. J. Org. Chem. https://doi.org/10.1002/ejoc.201901112 (2019).
doi: 10.1002/ejoc.201901112
Cao, S., Low, J., Yu, J. & Jaroniec, M. Polymeric photocatalysts based on graphitic carbon nitride. Adv. Mater. 27, 2150–2176 (2015).
pubmed: 25704586
doi: 10.1002/adma.201500033
Savateev, A. et al. Synthesis of an electronically modified carbon nitride from a processable semiconductor, 3-amino-1,2,4-triazole oligomer, via a topotactic-like phase transition. J. Mater. Chem. A 5, 8394–8401 (2017).
doi: 10.1039/C7TA01714F
Kisch, H. Semiconductor photocatalysis–mechanistic and synthetic aspects. Angew. Chem. Int. Ed. Engl. 52, 812–847 (2013).
pubmed: 23212748
doi: 10.1002/anie.201201200
Stephenson, C., Yoon, T. & MacMillan, D. W. C. Visible Light Photocatalysis in Organic Chemistry (Wiley, 2018).
Dvoranova, D., Barbierikova, Z. & Brezova, V. Radical intermediates in photoinduced reactions on TiO2 (an EPR spin trapping study). Molecules 19, 17279–17304 (2014).
pubmed: 25353381
pmcid: 6271711
doi: 10.3390/molecules191117279
Nagib, D. A. & Macmillan, D. W. C. Trifluoromethylation of arenes and heteroarenes by means of photoredox catalysis. Nature 480, 224–228 (2011).
pubmed: 22158245
pmcid: 3310175
doi: 10.1038/nature10647
Baar, M. & Blechert, S. Graphitic carbon nitride polymer as a recyclable photoredox catalyst for fluoroalkylation of arenes. Chem. Eur. J. 21, 526–530 (2015).
pubmed: 25413695
doi: 10.1002/chem.201405505
Zhao, Y., Shalom, M. & Antonietti, M. Visible light-driven graphitic carbon nitride (g-C3N4) photocatalyzed ketalization reaction in methanol with methylviologen as efficient electron mediator. Appl. Catal. B 207, 311–315 (2017).
doi: 10.1016/j.apcatb.2017.02.044
Filler, R., Kobayashi, Y. & Yagupolskii, L. Organofluorine Compounds in Medicinal Chemistry and Biomedical Applications (Elsevier Science LTD, 1993).
Zafrani, Y. et al. Difluoromethyl bioisostere: examining the “Lipophilic Hydrogen Bond Donor” concept. J. Med. Chem. 60, 797–804 (2017).
pubmed: 28051859
doi: 10.1021/acs.jmedchem.6b01691
Mai, V. H. & Nikonov, G. I. Hydrodefluorination of fluoroaromatics by isopropyl alcohol catalyzed by a ruthenium NHC complex. An unusual role of the carbene ligand. ACS Catal. 6, 7956–7961 (2016).
doi: 10.1021/acscatal.6b02004
Waghmode, S. B., Mahale, G., Patil, V. P., Renalson, K. & Singh, D. Efficient method for demethylation of aryl methyl ether using aliquat-336. Synth. Commun. 43, 3272–3280 (2013).
doi: 10.1080/00397911.2013.772201
Rebacz, N. A. & Savage, P. E. Anisole hydrolysis in high temperature water. Phys. Chem. Chem. Phys. 15, 3562–3569 (2013).
pubmed: 23381061
doi: 10.1039/c3cp43877e
Zhang, J., Xing, C., Tiwari, B. & Chi, Y. R. Catalytic activation of carbohydrates as formaldehyde equivalents for stetter reaction with enones. J. Am. Chem. Soc. 135, 8113–8116 (2013).
pubmed: 23688031
doi: 10.1021/ja401511r
Kohls, P., Jadhav, D., Pandey, G. & Reiser, O. Visible light photoredox catalysis: generation and addition of N -aryltetrahydroisoquinoline-derived α-amino radicals to michael acceptors. Org. Lett. 14, 672–675 (2012).
pubmed: 22260623
doi: 10.1021/ol202857t
Ruiz Espelt, L., Wiensch, E. M. & Yoon, T. P. Brønsted acid cocatalysts in photocatalytic radical addition of α-amino C–H bonds across michael acceptors. J. Org. Chem. 78, 4107–4114 (2013).
pubmed: 23537318
doi: 10.1021/jo400428m
Ruiz Espelt, L., McPherson, I. S., Wiensch, E. M. & Yoon, T. P. Enantioselective conjugate additions of α-amino radicals via cooperative photoredox and Lewis acid catalysis. J. Am. Chem. Soc. 137, 2452–2455 (2015).
pubmed: 25668687
doi: 10.1021/ja512746q
Murphy, J. J., Bastida, D., Paria, S., Fagnoni, M. & Melchiorre, P. Asymmetric catalytic formation of quaternary carbons by iminium ion trapping of radicals. Nature 532, 218–222 (2016).
pubmed: 27075098
doi: 10.1038/nature17438
Savateev, A. & Antonietti, M. Ionic carbon nitrides in solar hydrogen production and organic synthesis: exciting chemistry and economic advantages. ChemCatChem 11, 6166–6176 (2019).
doi: 10.1002/cctc.201901076
Cui, Q. et al. Phenyl-modified carbon nitride quantum dots with distinct photoluminescence behavior. Angew. Chem. Int. Ed. 55, 3672–3676 (2016).
doi: 10.1002/anie.201511217
Kurpil, B. et al. Hexaazatriphenylene doped carbon nitrides—biomimetic photocatalyst with superior oxidation power. Appl. Catal. B 217, 622–628 (2017).
doi: 10.1016/j.apcatb.2017.06.036
Kurpil, B., Markushyna, Y. & Savateev, A. Visible-light-driven reductive (Cyclo)dimerization of chalcones over heterogeneous carbon nitride photocatalyst. ACS Catal. 9, 1531–1538 (2019).
doi: 10.1021/acscatal.8b04182
Kurpil, B., Kumru, B., Heil, T., Antonietti, M. & Savateev, A. Carbon nitride creates thioamides in high yields by the photocatalytic Kindler reaction. Green. Chem. 20, 838–842 (2018).
doi: 10.1039/C7GC03734A
Savateev, A., Kurpil, B., Mishchenko, A., Zhang, G. & Antonietti, M. A. “waiting” carbon nitride radical anion: a charge storage material and key intermediate in direct C–H thiolation of methylarenes using elemental sulfur as the “S”-source. Chem. Sci. 9, 3584–3591 (2018).
pubmed: 29780491
pmcid: 5935028
doi: 10.1039/C8SC00745D
Kurpil, B. et al. Carbon nitride photocatalyzes regioselective aminium radical addition to the carbonyl bond and yields N-fused pyrroles. Nat. Commun. 10, 945–945 (2019).
pubmed: 30808862
pmcid: 6391478
doi: 10.1038/s41467-019-08652-w
Markushyna, Y. et al. Halogenation of aromatic hydrocarbons by halide anion oxidation with poly(heptazine imide) photocatalyst. Appl. Catal. B 248, 211–217 (2019).
doi: 10.1016/j.apcatb.2019.02.016
Ou, H., Tang, C., Chen, X., Zhou, M. & Wang, X. Solvated electrons for photochemistry syntheses using conjugated carbon nitride polymers. ACS Catal. 9, 2949–2955 (2019).
doi: 10.1021/acscatal.9b00314
Lau VWh et al. Dark photocatalysis: storage of solar energy in carbon nitride for time-delayed hydrogen generation. Angew. Chem. Int. Ed. 56, 510–514 (2017).
doi: 10.1002/anie.201608553
Plutschack, M. B., Pieber, B., Gilmore, K. & Seeberger, P. H. The Hitchhiker’s guide to flow chemistry. Chem. Rev. 117, 11796–11893 (2017).
pubmed: 28570059
doi: 10.1021/acs.chemrev.7b00183
Movsisyan, M. et al. Taming hazardous chemistry by continuous flow technology. Chem. Soc. Rev. 45, 4892–4928 (2016).
pubmed: 27453961
doi: 10.1039/C5CS00902B
Woźnica, M., Chaoui, N., Taabache, S. & Blechert, S. THF: an efficient electron donor in continuous flow radical cyclization photocatalyzed by graphitic carbon nitride. Chem. Eur. J. 20, 14624–14628 (2014).
pubmed: 25252017
doi: 10.1002/chem.201404440
Bajada M. et al. Visible light flow reactor packed with porous carbon nitride for aerobic substrate oxidations. ACS Appl. Mater. Interfaces https://doi.org/10.1021/acsami.9b19718 (2020).
doi: 10.1021/acsami.9b19718
Rodríguez, N. A., Savateev, A., Grela, M. A. & Dontsova, D. Facile synthesis of potassium poly(heptazine imide) (PHIK)/Ti-based metal–organic framework (MIL-125-NH2) composites for photocatalytic applications. ACS Appl. Mater. Interfaces 9, 22941–22949 (2017).
pubmed: 28609616
doi: 10.1021/acsami.7b04745
Krivtsov, I. et al. Water-soluble polymeric carbon nitride colloidal nanoparticles for highly selective quasi-homogeneous photocatalysis. Angew. Chem. Int. Ed. 59, 487–495 (2020).
doi: 10.1002/anie.201913331
Jones, W. et al. A comparison of photocatalytic reforming reactions of methanol and triethanolamine with Pd supported on titania and graphitic carbon nitride. Appl. Catal. B 240, 373–379 (2019).
doi: 10.1016/j.apcatb.2017.01.042
Zhang, G. et al. Electron deficient monomers that optimize nucleation and enhance the photocatalytic redox activity of carbon nitrides. Angew. Chem. Int. Ed. 58, 14950–14954 (2019).
doi: 10.1002/anie.201908322
Samanta, S., Khilari, S., Pradhan, D. & Srivastava, R. An efficient, visible light driven, selective oxidation of aromatic alcohols and amines with O2 using BiVO4/g-C3N4 nanocomposite: a systematic and comprehensive study toward the development of a photocatalytic process. ACS Sustain. Chem. Eng. 5, 2562–2577 (2017).
doi: 10.1021/acssuschemeng.6b02902
Chen, Z. et al. “The Easier the Better” preparation of efficient photocatalysts-metastable poly(heptazine imide) salts. Adv. Mater. 29, 1700555 (2017).
doi: 10.1002/adma.201700555
Maruoka, K., Shimada, I., Imoto, H. & Yamamoto, H. Conjugate addition of reactive carbanions to α,β-unsaturated ketones in the presence of ATPH. Synlett 1994, 519–520 (1994).
doi: 10.1055/s-1994-22912
Serpone, N. Relative photonic efficiencies and quantum yields in heterogeneous photocatalysis. J. Photochem. Photobiol. A 104, 1–12 (1997).
doi: 10.1016/S1010-6030(96)04538-8
Francesconi, I. et al. 2,4-Diphenyl furan diamidines as novel anti-Pneumocystis carinii pneumonia agents. J. Med. Chem. 42, 2260–2265 (1999).
pubmed: 10377232
doi: 10.1021/jm990071c
Thompson, B. B. & Montgomery, J. Enone-alkyne reductive coupling: a versatile entry to substituted pyrroles. Org. Lett. 13, 3289–3291 (2011).
pubmed: 21657241
doi: 10.1021/ol201133n
Su, F. et al. Aerobic oxidative coupling of amines by carbon nitride photocatalysis with visible light. Angew. Chem. Int. Ed. Engl. 50, 657–660 (2011).
pubmed: 21226146
doi: 10.1002/anie.201004365
Hu, X. Q. et al. Catalytic N-radical cascade reaction of hydrazones by oxidative deprotonation electron transfer and TEMPO mediation. Nat. Commun. 7, 11188 (2016).
pubmed: 27048886
pmcid: 4823831
doi: 10.1038/ncomms11188