Home Visible-light-mediated metal-free C–Si bond formation reactions
Article
Licensed
Unlicensed Requires Authentication

Visible-light-mediated metal-free C–Si bond formation reactions

  • Sumit Ghosh and Alakananda Hajra ORCID logo EMAIL logo
Published/Copyright: February 23, 2022
Become an author with De Gruyter Brill

Abstract

Conserving the environment is one of the most imperative goals in recent days among the chemists throughout the world. Swiftly increasing the environmental awareness also increases the demand to build new approaches for synthesizing the same active molecules with zero-waste and pollution. In this background, visible-light-mediated synthesis and functionalization of diverse organic compounds has been established as a tremendously successful topic and has achieved a remarkable stage of superiority and efficiency in the last 20 years. Alternatively, organosilicon derivatives are gradually aspiring leaves among chemists because of their significant application on synthetic, medicinal, and material chemistry. In this scenario, the addition of Si–H group to carbon−carbon multiple bonds (alkenes, hetero-arenes, alkynes, allenes, carboxylic acids, enynes, and dienes) provides an extremely step- and atom-efficient method to obtain silicon-containing compounds. Several attempts for the development of mild, robust, and efficient green protocol were taken in the last two decades. In spite of substantial advancement/research on C–Si bond formation using transition metal catalysis, a green and metal-free approach is highly essential considering its application in the field of medicine and with respect to environmental aspects as well. In this article, we will summarize the reports considering suitable visible-light-mediated metal-free silylation of C–C multiple bonds that includes alkenes, hetero-arenes, alkynes, allenes, enynes, and dienes.


Corresponding author: Alakananda Hajra, Department of Chemistry, Visva-Bharati (A Central University), Santiniketan 731235, India, E-mail:

  1. Author contribution: All authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: A. H. acknowledges the financial support from CSIR, New Delhi (Grant No. 02(0455)/21/EMR-II).

  3. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

References

1. Brook, MA. Silicon in organic, organometallic, and polymer chemistry. New York: Wiley-Interscience; 1999.Search in Google Scholar

2. Denmark, SE, Sweis, RF. Design and implementation of new, silicon-based, cross-coupling reactions: importance of silicon−oxygen bonds. Acc Chem Res 2002;35:835–46.10.1021/ar020001rSearch in Google Scholar PubMed

3. Mills, JS, Showell, GA. Exploitation of silicon medicinal chemistry in drug discovery. Expet Opin Invest Drugs 2004;13:1149–57.10.1517/13543784.13.9.1149Search in Google Scholar PubMed

4. Franz, AK, Wilson, SO. Organosilicon molecules with medicinal applications. J Med Chem 2013;56:388–405.10.1021/jm3010114Search in Google Scholar PubMed

5. Lukevics, E, Abele, E, Ignatovich, L. Chapter 4 - biologically active silacyclanes. In: Katritzky, AR, editor. Adv heterocycl chem. San Diego: Academic Press, vol 99. pp. 107–41. 2010.10.1016/S0065-2725(10)09904-6Search in Google Scholar

6. Colvin, EW. Preparation and use of organosilicon compounds in organic synthesis. In: Hartley, FR, editor The metal—carbon bond; 1987. pp. 539–622.10.1002/9780470771778.ch6Search in Google Scholar

7. Shi, H, Yang, J, Li, Z, He, C. Introduction of organosilicon materials; silicon containing hybrid copolymers; 2020. p. 1–21.10.1002/9783527823499.ch1Search in Google Scholar

8. Strohmann, C, Lüdtke, S, Wack, E. New bis(lithiomethyl)silanes: building blocks for organosilanes. Chem Ber 1996;129:799–805.10.1002/cber.19961290710Search in Google Scholar

9. Geyer, M, Karlsson, O, Baus, JA, Wellner, E, Tacke, R. Si- and C-functional organosilicon building blocks for synthesis based on 4-silacyclohexan-1-ones containing the silicon protecting groups MOP (4-methoxyphenyl), DMOP (2,6-dimethoxyphenyl), or TMOP (2,4,6-trimethoxyphenyl). J Org Chem 2015;80:5804–11.10.1021/acs.joc.5b00774Search in Google Scholar PubMed

10. Strohmann, C, Lüdtke, S, Ulbrich, O. Tris- and tetrakis(lithiomethyl)silanes: an easy access to new building blocks for organosilicon compounds. Organometallics 2000;19:4223–7.10.1021/om000596zSearch in Google Scholar

11. Cypes, SH, Saltzman, WM, Giannelis, EP. Organosilicate-polymer drug delivery systems: controlled release and enhanced mechanical properties. J Contr Release 2003;90:163–9.10.1016/S0168-3659(03)00133-0Search in Google Scholar PubMed

12. Richter, R, Roewer, G, Böhme, U, Busch, K, Babonneau, F, Martin, HP, et al.. Organosilicon polymers—synthesis, architecture, reactivity and applications. Appl Organomet Chem 1997;11:71–106.10.1002/(SICI)1099-0739(199702)11:2<71::AID-AOC562>3.0.CO;2-NSearch in Google Scholar

13. Thames, SF, Panjnani, KG. Organosilane polymer chemistry: a review. J Inorg Organomet Polym 1996;6:59–94.10.1007/BF01098320Search in Google Scholar

14. Uhlig, W. Synthesis, functionalization, and cross-linking reactions of organosilicon polymers using silyl triflate intermediates. Prog Polym Sci 2002;27:255–305.10.1016/S0079-6700(01)00052-1Search in Google Scholar

15. Pooni, PK, Showell, GA. Silicon switches of marketed drugs. Mini Rev Med Chem 2006;6:1169–77.10.2174/138955706778560120Search in Google Scholar

16. Häbich, D, Effenberger, F. Preparation of Aryl- and Heteroaryltrimethylsilanes. Synthesis 1979;1979:841–76.10.1055/s-1979-28855Search in Google Scholar

17. Wilkinson, JR, Nuyen, CE, Carpenter, TS, Harruff, SR, Van Hoveln, R. Copper-catalyzed carbon–silicon bond formation. ACS Catal 2019;9:8961–79.10.1021/acscatal.9b02762Search in Google Scholar

18. Huang Hongtai, LT, Jiazhuang, W, Guiping, Q, Tiebo, X. Recent advance in transition-metal-catalyzed silylation of C-H bonds. Chin J Org Chem 2019;39:1511–21.10.6023/cjoc201903078Search in Google Scholar

19. Wang Mingfeng, YM, Wenshu, W, Weili, L, Feixian, L. Cross-coupling of C-Si bond by using silyl reagents. Chin J Org Chem 2019;39:3145–53.10.6023/cjoc201904024Search in Google Scholar

20. Zhou, B, Lu, A, Zhang, Y. Pd-catalyzed C–H silylation reactions with disilanes. Synlett 2019;30:685–93.10.1055/s-0037-1610339Search in Google Scholar

21. Xu, L, Zhang, S, Li, P. Synthesis of silafluorenes and silaindenes via silyl radicals from arylhydrosilanes: intramolecular cyclization and intermolecular annulation with alkynes. Org Chem Front 2015;2:459–63.10.1039/C5QO00012BSearch in Google Scholar

22. Lin, Y-m, Lu, G-p, Wang, R-k, Yi, W-b. Stereoselective synthesis of alkenyl silanes, sulfones, phosphine oxides, and nitroolefins by radical C–S bond cleavage of arylalkenyl sulfides. Org Lett 2017;19:1100–3.10.1021/acs.orglett.7b00126Search in Google Scholar PubMed

23. Zhang, X, Fang, J, Cai, C, Lu, G. Recent advances in synthesis of organosilicons via radical strategies. Chin Chem Lett 2020;32:1280–92.10.1016/j.cclet.2020.09.058Search in Google Scholar

24. Xuan, J, Xiao, W-J. Visible-light photoredox catalysis. Angew Chem Int Ed 2012;51:6828–38.10.1002/anie.201200223Search in Google Scholar PubMed

25. Revathi, L, Ravindar, L, Fang, W-Y, Rakesh, KP, Qin, H-L. Visible light-induced C−H bond functionalization: a critical review. Adv Synth Catal 2018;360:4652–98.10.1002/adsc.201800736Search in Google Scholar

26. Narayanam, JMR, Stephenson, CRJ. Visible light photoredox catalysis: applications in organic synthesis. Chem Soc Rev 2011;40:102–13.10.1039/B913880NSearch in Google Scholar

27. Yoon, TP, Ischay, MA, Du, J. Visible light photocatalysis as a greener approach to photochemical synthesis. Nat Chem 2010;2:527–32.10.1038/nchem.687Search in Google Scholar PubMed

28. Stephenson, C, Yoon, T, MacMillan, DWC. Visible light photocatalysis in organic chemistry; 2018.10.1002/9783527674145Search in Google Scholar

29. Prier, CK, Rankic, DA, MacMillan, DWC. Visible light photoredox catalysis with transition metal complexes: applications in organic synthesis. Chem Rev 2013;113:5322–63.10.1021/cr300503rSearch in Google Scholar PubMed PubMed Central

30. Shaw, MH, Twilton, J, MacMillan, DWC. Photoredox catalysis in organic chemistry. J Org Chem 2016;81:6898–926.10.1021/acs.joc.6b01449Search in Google Scholar PubMed PubMed Central

31. MacMillan, DWC. The advent and development of organocatalysis. Nature 2008;455:304–8.10.1038/nature07367Search in Google Scholar PubMed

32. Twilton, J, Le, C, Zhang, P, Shaw, MH, Evans, RW, MacMillan, DWC. The merger of transition metal and photocatalysis. Nat Rev Chem 2017;1:0052.10.1038/s41570-017-0052Search in Google Scholar

33. Ghosh, S, Lai, D, Hajra, A. Visible-light-induced silylation: an update. Org Biomol Chem 2021;19:2399–415.10.1039/D1OB00082ASearch in Google Scholar PubMed

34. Bagdi, AK, Rahman, M, Bhattacherjee, D, Zyryanov, GV, Ghosh, S, Chupakhin, ON, et al.. Visible light promoted cross-dehydrogenative coupling: a decade update. Green Chem 2020;22:6632–81.10.1039/D0GC02437FSearch in Google Scholar

35. Neogi, S, Ghosh, AK, Majhi, K, Samanta, S, Kibriya, G, Hajra, A. Organophotoredox-catalyzed direct C–H amination of 2H-indazoles with amines. Org Lett 2020;22:5605–9.10.1021/acs.orglett.0c01973Search in Google Scholar PubMed

36. Kibriya, G, Ghosh, D, Hajra, A. Visible-light-promoted oxidative coupling of styrene with cyclic ethers. Sci China Chem 2020;63:42–6.10.1007/s11426-019-9609-9Search in Google Scholar

37. Bhattacharjee, S, Laru, S, Samanta, S, Singsardar, M, Hajra, A. Visible light-induced photocatalytic C–H ethoxycarbonylmethylation of imidazoheterocycles with ethyl diazoacetate. RSC Adv 2020;10:27984–8.10.1039/D0RA05795ASearch in Google Scholar

38. Bagdi, AK, Hajra, A. Visible light promoted C–H functionalization of imidazoheterocycles. Org Biomol Chem 2020;18:2611–31.10.1039/D0OB00246ASearch in Google Scholar

39. Singsardar, M, Mondal, S, Laru, S, Hajra, A. Organophotoredox-catalyzed C(sp2)–H difluoromethylenephosphonation of imidazoheterocycles. Org Lett 2019;21:5606–10.10.1021/acs.orglett.9b01954Search in Google Scholar PubMed

40. Singsardar, M, Laru, S, Mondal, S, Hajra, A. Visible-light-induced regioselective cross-dehydrogenative coupling of 2H-indazoles with ethers. J Org Chem 2019;84:4543–50.10.1021/acs.joc.9b00318Search in Google Scholar PubMed

41. De, A, Santra, S, Hajra, A, Zyryanov, GV, Majee, A. Visible-light-induced regioselective C(sp3)-H acyloxylation of aryl-2H azirines with (diacetoxy)iodobenzene. J Org Chem 2019;84:11735–40.10.1021/acs.joc.9b01625Search in Google Scholar PubMed

42. Singsardar, M, Dey, A, Sarkar, R, Hajra, A. Visible-light-induced organophotoredox-catalyzed phosphonylation of 2H-indazoles with diphenylphosphine oxide. J Org Chem 2018;83:12694–701.10.1021/acs.joc.8b02019Search in Google Scholar PubMed

43. Kibriya, G, Mondal, S, Hajra, A. Visible-light-mediated synthesis of unsymmetrical diaryl sulfides via oxidative coupling of arylhydrazine with thiol. Org Lett 2018;20:7740–3.10.1021/acs.orglett.8b03549Search in Google Scholar PubMed

44. Kibriya, G, Bagdi, AK, Hajra, A. Visible light induced tetramethylethylenediamine assisted formylation of imidazopyridines. Org Biomol Chem 2018;16:3473–8.10.1039/C8OB00532JSearch in Google Scholar PubMed

45. Kibriya, G, Bagdi, AK, Hajra, A. Visible-light-promoted C(sp3)–C(sp2) cross-dehydrogenative coupling of tertiary amine with imidazopyridine. J Org Chem 2018;83:10619–26.10.1021/acs.joc.8b01433Search in Google Scholar PubMed

46. Kibriya, G, Samanta, S, Jana, S, Mondal, S, Hajra, A. Visible light organic photoredox-catalyzed C–H alkoxylation of imidazopyridine with alcohol. J Org Chem 2017;82:13722–7.10.1021/acs.joc.7b02582Search in Google Scholar PubMed

47. Lai, D, Ghosh, S, Hajra, A. Light-induced borylation: developments and mechanistic insights. Org Biomol Chem 2021;19:4397–428.10.1039/D1OB00323BSearch in Google Scholar PubMed

48. Neogi, S, Kumar Ghosh, A, Mandal, S, Ghosh, D, Ghosh, S, Hajra, A. Three-component carbosilylation of alkenes by merging iron and visible-light photocatalysis. Org Lett 2021;23:6510–4.10.1021/acs.orglett.1c02322Search in Google Scholar PubMed

49. Matsumoto, A, Ito, Y. New generation of organosilyl radicals by photochemically induced homolytic cleavage of silicon−boron bonds. J Org Chem 2000;65:5707–11.10.1021/jo000547wSearch in Google Scholar PubMed

50. Zhou, R, Goh, YY, Liu, H, Tao, H, Li, L, Wu, J. Visible-light-mediated metal-free hydrosilylation of alkenes through selective hydrogen atom transfer for Si−H activation. Angew Chem Int Ed 2017;56:16621–5.10.1002/anie.201711250Search in Google Scholar PubMed

51. Hou, J, Ee, A, Cao, H, Ong, H-W, Xu, J-H, Wu, J. Visible-light-mediated metal-free difunctionalization of alkenes with CO2 and silanes or C(sp3)−H alkanes. Angew Chem Int Ed 2018;57:17220–4.10.1002/anie.201811266Search in Google Scholar PubMed

52. Zhu, J, Cui, W-C, Wang, S, Yao, Z-J. Visible light-driven radical trans-hydrosilylation of electron-neutral and -rich alkenes with tertiary and secondary hydrosilanes. J Org Chem 2018;83:14600–9.10.1021/acs.joc.8b02409Search in Google Scholar PubMed

53. Liu, R, Chia, SPM, Goh, YY, Cheo, HW, Fan, B, Li, R, et al.. Visible-light-mediated regioselective allylation, benzylation, and silylation of methylene-malononitriles via photoredox-induced radical cation fragmentation. Eur J Org Chem 2020;2020:1459–65.10.1002/ejoc.201900902Search in Google Scholar

54. Xu, N-X, Li, B-X, Wang, C, Uchiyama, M. Sila- and germacarboxylic acids: precursors for the corresponding silyl and germyl radicals. Angew Chem Int Ed 2020;59:10639–44.10.1002/anie.202003070Search in Google Scholar PubMed

55. Becker, P, Priebbenow, DL, Zhang, H-J, Pirwerdjan, R, Bolm, C. Photochemical intermolecular silylacylations of electron-deficient internal alkynes. J Org Chem 2014;79:814–7.10.1021/jo402457xSearch in Google Scholar PubMed

56. Zhu, J, Cui, W-C, Wang, S, Yao, Z-J. Radical hydrosilylation of alkynes catalyzed by eosin Y and thiol under visible light irradiation. Org Lett 2018;20:3174–8.10.1021/acs.orglett.8b00909Search in Google Scholar PubMed

57. Cai, Y, Zhao, W, Wang, S, Liang, Y, Yao, Z-J. Access to functionalized E-allylsilanes and E-alkenylsilanes through visible-light-driven radical hydrosilylation of mono- and disubstituted allenes. Org Lett 2019;21:9836–40.10.1021/acs.orglett.9b03679Search in Google Scholar PubMed

58. Yang, C, Wang, J, Li, J, Ma, W, An, K, He, W, et al.. Visible-light induced radical silylation for the synthesis of dibenzosiloles via dehydrogenative cyclization. Adv Synth Catal 2018;360:3049–54.10.1002/adsc.201800417Search in Google Scholar

59. Dai, C, Zhan, Y, Liu, P, Sun, P. Organic photoredox catalyzed C–H silylation of quinoxalinones or electron-deficient heteroarenes under ambient air conditions. Green Chem 2021;23:314–9.10.1039/D0GC03697HSearch in Google Scholar

60. Cui, W-C, Zhao, W, Gao, M, Liu, W, Wang, S, Liang, Y, et al.. Diastereoselective synthesis of polysubstituted piperidines through visible-light-driven silylative cyclization of aza-1,6-dienes: experimental and DFT studies. Chem Eur J 2019;25:16506–10.10.1002/chem.201903440Search in Google Scholar PubMed

Published Online: 2022-02-23

© 2022 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Frontmatter
  2. Reviews
  3. Recent endeavors in microbial remediation of micro- and nanoplastics
  4. Metal nanoparticles and its application on phenolic and heavy metal pollutants
  5. The story of nitrogen
  6. Recent development of imidazole derivatives as potential anticancer agents
  7. Indole based prostate cancer agents
  8. Lawsone (2-hydroxy-1,4-naphthaquinone) derived anticancer agents
  9. Small modular nuclear reactors are mostly bad policy
  10. A holistic environmental investigation of complementary energy in Alberta
  11. Green synthesis of various saturated S-heterocyclic scaffolds: an update
  12. Recent advances of heterocycle based anticancer hybrids
  13. Molecular docking and MD: mimicking the real biological process
  14. Synthesis of quinazolinone and quinazoline derivatives using green chemistry approach
  15. Nuclear fusion: the promise of endless energy
  16. Finance for Green Chemistry through Currency Mix
  17. Synthesis of bioactive scaffolds catalyzed by agro-waste-based solvent medium
  18. Recent developments in the green synthesis of biologically relevant cinnolines and phthalazines
  19. Detection of Rapid Eye Movement Behaviour Sleep Disorder using Time and Frequency Analysis of EEG Signal Applied on C4-A1 Channels
  20. Recent developments in C–C bond formation catalyzed by solid supported palladium: a greener perspective
  21. Visible-light-mediated metal-free C–Si bond formation reactions
  22. An overview of quinoxaline synthesis by green methods: recent reports
  23. Naturally occurring, natural product inspired and synthetic heterocyclic anti-cancer drugs
  24. Synthesis of bioactive natural products and their analogs at room temperature – an update
  25. One-pot multi-component synthesis of diverse bioactive heterocyclic scaffolds involving 6-aminouracil or its N-methyl derivatives as a versatile reagent
  26. Synthesis of new horizons in benzothiazole scaffold and used in anticancer drug development
  27. Triazine based chemical entities for anticancer activity
  28. Modification of kaolinite/muscovite clay for the removal of Pb(II) ions from aqueous media
  29. In silico design of ACE2 mutants for competitive binding of SARS-CoV-2 receptor binding domain with hACE2
  30. Computational study of Cu n AgAu (n = 1–4) clusters invoking DFT based descriptors
  31. Development of an online assessment system to evaluate knowledge on chemical safety and security
  32. Developing a questionnaire for diabetes mellitus type 2 risk effects and precondition factors – multivariate statistical paths
  33. Antioxidant and antibacterial activities of two xanthones derivatives isolated from the leaves extract of Anthocleista schweinfurthii Gilg (Loganiaceae)
  34. The stability increase of α-amylase enzyme from Aspergillus fumigatus using dimethyladipimidate
  35. Sustainability of ameliorative potentials of urea spiked poultry manure biochar types in simulated sodic soils
  36. Cytotoxicity test and antibacterial assay on the compound produced by the isolation and modification of artonin E from Artocarpus kemando Miq.
  37. Effects of alum, soda ash, and carbon dioxide on 40–50 year old concrete wastewater tanks
Downloaded on 11.9.2025 from https://www.degruyterbrill.com/document/doi/10.1515/psr-2021-0087/html
Scroll to top button