Citation: Zhang Ben-Hou, Kong Jing-Jing, Huang Yang, Lou Yue-Guang, Li Xiao-Fei, He Chun-Yang. Benign perfluoroalkylation of uracils and uracil nucleosides via visible light-induced photoredox catalysis[J]. Chinese Chemical Letters, ;2017, 28(8): 1751-1754. doi: 10.1016/j.cclet.2017.03.039 shu

Benign perfluoroalkylation of uracils and uracil nucleosides via visible light-induced photoredox catalysis

a.
School of Pharmacy, Zunyi Medical University, Zunyi 563003, China
b.
Dafeng Marine Industrial Institute of Nanjing Tech University, Yancheng 224145, China

Corresponding author: Li Xiao-Fei, lixiaofei@zmu.edu.cn He Chun-Yang, hechy2002@163.com

Received Date: 21 January 2017
Revised Date: 28 February 2017
Accepted Date: 22 March 2017
Available Online: 9 August 2017

Figures(4)

In this work, an efficient and facile method for the preparation of 5-perfluoroalkylated uracils and uracil nucleosides through visible-light-mediated reaction has been developed. The reaction processes in high efficiency under mild reaction conditions and show broad substrate scope by employing commercial available perfluoroalkyl sources, thus demonstrates high potent application in life and medicinal science.
- Uracils,
- Uracil Nucleosides,
- Blue LED,
- Photoredox catalysis,
- Perfluoroalkylation
1. [1]
  Agrofoglio L.A., Gillaizeau I., Saito Y.. Palladium-assisted routes to nucleosides[J]. Chem. Rev., 2003,103:1875-1916. doi: 10.1021/cr010374q
2. [2]
  De Clercq E., Descamps J., De Somer P.. (E)-5-(2-Bromovinyl)-2'-deoxyuridine:a potent and selective anti-herpes agent[J]. Proc. Natl. Acad. Sci. U. S. A., 1979,76:2947-2951. doi: 10.1073/pnas.76.6.2947
3. [3]
  McGuigan C., Barucki H., Blewett S.. Highly potent and selective inhibition of varicella-zoster virus by bicyclic furopyrimidine nucleosides bearing an aryl side chain[J]. J. Med. Chem., 2000,43:4993-4997. doi: 10.1021/jm000210m
4. [4]
  Heidenreich J.O., Pieken W., Eckstein F.. Chemically modified RNA:approaches and applications[J]. FASEBJournal, 1993,7:90-96.
5. [5]
  Pallan J.P.S., Greene E.M., Jicman P.A.. Unexpected origins of the enhanced pairing affinity of 2'-fluoro-modified RNA[J]. Nucleic Acids Res., 2011,39:3482-3495. doi: 10.1093/nar/gkq1270
6. [6]
  Košutić M., Jud L., Da Veiga C.. Surprising base pairing and structural properties of 2'-trifluoromethylthio-modified ribonucleic acids[J]. J. Am. Chem. Soc., 2014,136:6656-6663. doi: 10.1021/ja5005637
7. [7]
  R.D. Chambers, Fluorine in Organic Chemistry, 2th ed, Blackwell, London, 2004.
8. [8]
  P. Kirsh, Modern Fluoroorganic Chemistry, Wiley-VCH, Weinheim, 2004.
9. [9]
  J.T. Welch, S. Eswarakrishnan, Fluorine inbioorganic Chemistry, Wiley, New York, 1991.
10. [10]
  Metterle L., Nelson C., Patel N.. Intralesional 5-fluorouracil (FU) as a treatment for nonmelanoma skin cancer (NMSC):A review[J]. J. Am. Acad.of Dermatol., 2015,74:552-557.
11. [11]
  Carrillo E., Navarro S.A., Ramirez A.. 5-Fluorouracil derivatives:a patent review (2012-2014)[J]. Expert. Opin. Ther. Pat., 2015,25:1131-1144. doi: 10.1517/13543776.2015.1056736
12. [12]
  Palasz A., Ciez D.. The driving force:digital servo drive doubles accuracy of high-speed cut-to-length machines[J]. Eur. J. Med. Chem., 2015,46:582-611.
13. [13]
  Lenz H.J., Stintzing S., Loupakis F.. TAS-102, a novel antitumor agent:A review of the mechanism of action[J]. Cancer Treat. Rev., 2015,41:777-783. doi: 10.1016/j.ctrv.2015.06.001
14. [14]
  De Clercq E.. Selective anti-herpesvirus agents[J]. Antivir. Chem. Chemoth., 2013,23:93-101. doi: 10.3851/IMP2533
15. [15]
  Caillot G., Dufour J., Belhomme M.C.. Copper-catalyzed olefinic C-H difluoroacetylation of enamides[J]. Chem. Commun., 2014,50:5887-5890. doi: 10.1039/C4CC01994F
16. [16]
  Sladojevich F., McNeill E., Boergel J., Zheng S.L., Ritter T.. Condensed-phase, halogen-bonded CF₃I and C₂F₅I adducts for perfluoroalkylation reactions[J]. Angew. Chem. Int. Ed., 2015,54:3712-3716. doi: 10.1002/anie.201410954
17. [17]
  Ivanova M., Bayle A., Besset T., Poisson T., Pannecoucke X.. Copper saltcontrolled divergent reactivity of[J]. Angew. Chem. Int. Ed., 2016,55:14141-14145. doi: 10.1002/anie.v55.45
18. [18]
  Aikawa K., Nakamura Y., Yokota Y., Toya W., Mikami K.. Stable but reactive perfluoroalkylzinc reagents:application in ligand-free copper-catalyzed perfluoroalkylation of aryl iodides[J]. Chem. Eur. J., 2015,21:96-100. doi: 10.1002/chem.201405677
19. [19]
  Zhao Y., Zhao B., Liu J.. Oxide-modified nickel photocatalysts for the production of hydrocarbons in visible light[J]. Angew. Chem. Int. Ed, 2016,55:4215-4219. doi: 10.1002/anie.201511334
20. [20]
  Yu H., Shi R., Zhao Y.. Smart utilization of carbon dots in semiconductor photocatalysis[J]. Adv. Mater., 2016,28:9454-9477. doi: 10.1002/adma.201602581
21. [21]
  Zhao Y., Jia X., Waterhouse G.I.N.. Layered double hydroxide nanostructured photocatalysts for renewable energy production[J]. Adv. Energy. Mater., 2016,6. doi: 10.1002/aenm.201501974
22. [22]
  Zhao Y., Chen G., Bian T.. Defect-rich ultrathinznal-layered double hydroxide nanosheets for efficient photoreduction of CO₂ to CO with water[J]. Adv. Mater., 2015,27:7824-7831. doi: 10.1002/adma.201503730
23. [23]
  Min Q.Q., Yin Z., Feng Z., Guo W.H., Zhang X.. Highly selective gemdifluoroallylation of organoborons with bromodifluoromethylated alkenes catalyzed by palladium[J]. J. Am. Chem. Soc., 2014,136:1230-1233. doi: 10.1021/ja4114825
24. [24]
  Feng Z., Min Q.Q., Zhao H.Y., Gu J.W., Zhang X.. A general synthesis of fluoroalkylated alkenes by palladium-catalyzed heck-type reaction of fluoroalkyl bromides[J]. Angew. Chem. Int. Ed., 2015,54:1270-1274. doi: 10.1002/anie.201409617
25. [25]
  Ge S., Chaladaj W., Hartwig J.F.. Pd-Catalyzed(-arylation of (, (-difluoroketones with aryl bromides and chlorides A route to difluoromethylarenes[J]. J. Am. Chem. Soc., 2014,136:4149-4152. doi: 10.1021/ja501117v
26. [26]
  Guo C., Wang R.W., Qing F.L.. Palladium catalyzed direct(-arylation of (, (-difluoroketones with aryl bromides[J]. J. Fluorine Chem., 2013,44:135-142.
27. [27]
  Feng Z., Chen F., Zhang X.. Copper catalyzed cross-coupling of iodobenzoates with bromozincdifluorophosphonate[J]. Org. Lett., 2012,14:1938-1941. doi: 10.1021/ol3006425
28. [28]
  Chatterjee T., Iqbal N., You Y., Cho E.J.. Controlled fluoroalkylation reactions by visible-light photoredox catalysis[J]. Acc. Chem. Res., 2016,49:2284-2294. doi: 10.1021/acs.accounts.6b00248
29. [29]
  Tang X.J., Dolbier W.R.. Efficient Cu-catalyzed atom transfer radical addition (ATRA) reactions of fluoroalkylsulfonyl chlorides with electron-deficient alkenes induced by visible light[J]. Angew. Chem. Int. Ed., 2015,54:4246-4249. doi: 10.1002/anie.201412199
30. [30]
  Li W., Zhu X., Mao H.. Visible-light-induced direct C(sp3)-H difluromethylation of tetrahydroisoquinolines with the in situ generated difluoroenolates[J]. Chem. Commun., 2014,50:7521-7523. doi: 10.1039/C4CC02768J
31. [31]
  Su Y.M., Hou Y., Yin F.. VisibleLight-Mediated C-H difluoromethylation of electron-rich heteroarenes[J]. Org. Lett., 2014,16:2958-2961. doi: 10.1021/ol501094z
32. [32]
  Lin Q., Chu L., Qing F.. Direct introduction of ethoxycarbonyldifluoromethyl-Group to heteroarenes with ethyl bromodifluoroacetate via visible-Light photocatalysis[J]. Chin. J. Chem., 2013,45:885-891.
33. [33]
  Nguyen J.D., Tucker J.W., Konieczynska M.D., Stephenson C.R.J.. Intermolecular Atom transfer radical addition to olefins mediated by oxidative quenching of photoredox catalysts[J]. J. Am. Chem. Soc., 2011,133:4160-4163. doi: 10.1021/ja108560e
34. [34]
  He C.Y., Kong J., Li X.. Visible-Light-Induced direct difluoroalkylation of uracils, pyridinones and coumarins[J]. J. Org. Chem., 2017,82:910-917. doi: 10.1021/acs.joc.6b02316
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1.
沈阳化工大学材料科学与工程学院沈阳 110142