Skip to main content

Environment-Friendly Iron-Catalyzed Reactions

  • Chapter
  • First Online:
  • 1188 Accesses

Abstract

Aromatics composed of benzene, naphthalene, heteroarene etc., are useful backbones in various scientific fields, such as the pharmaceutical and material chemistries. Iron (Fe) metal is one of the bountiful resources on the earth and iron trichloride (FeCl3) is widely utilized as an inexpensive and commercially available reagent for organic synthesis. Meanwhile, the reactions generating neutral wastes and/or reducing wastes are valuable methods from the viewpoint of green chemistry. We have continuously investigated the FeCl3-catalyzed benzylic activations of various substrates to construct highly-functionalized aromatics. The reactions that only generate water, methanol or silanol derived from substrates as a neutral waste are regarded to be environmentally friendly and green sustainable in comparison with the similar reported reactions, which generate acidic waste and/or require the use of rare metals. In this review, our recent results, related to the chemo-selective transformations and construction of highly-substituted aromatics, etc., are summarized.

This is a preview of subscription content, log in via an institution.

Buying options

Chapter
USD   29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD   149.00
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD   199.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD   199.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Learn about institutional subscriptions

References

  1. Wuts P. G. M.; Greene T. W., “Greene’s Protective Groups in Organic Synthesis”, 5th Edition, Wiley, Hoboken, (2007).

    Google Scholar 

  2. Sawama, Y.; Nagata, S.; Yabe, Y.; Morita, K.; Monguchi, Y.; Sajiki, H., “Iron-Catalyzed Chemoselective Azidation of Benzylic Silyl Ethers”, Chem. Eur. J. (2012) 18, 16608–16611.

    Google Scholar 

  3. Niggemann, M.; Meel, M. J., “Calcium-Catalyzed Friedel–Crafts Alkylation at Room Temperature”, Angew. Chem. Int. Ed. (2010) 49, 3684–3687.

    Google Scholar 

  4. Iovel, I.; Mertins, K.; Kischel, J.; Zapf, A.; Beller, M., “An Efficient and General Iron-Catalyzed Arylation of Benzyl Alcohols and Benzyl Carboxylates”, Angew. Chem. Int. Ed. (2005) 44, 3913–3917.

    Google Scholar 

  5. Schäfer, G.; Bode, J. W., “Friedel–Crafts Benzylation of Activated and Deactivated Arenes”, Angew. Chem. Int. Ed. (2011) 50, 10913–10916.

    Google Scholar 

  6. Sawama, Y.; Shishido, Y.; Kawajiri, T.; Goto, R.; Monguchi, Y.; Sajiki, H., “Iron-Catalyzed Friedel-Crafts Benzylation with Benzyl TMS Ethers at Room Temperature”, Chem. Eur. J. (2014) 20, 510–516.

    Google Scholar 

  7. Nokami, T.; Ohata, K.; Inoue, M.; Tsuyama, H.; Shibuya, A.; Soga, K.; Okajima, M.; Suga, S.; Yoshida, J., “Iterative Molecular Assembly Based on the Cation-Pool Method. Convergent Synthesis of Dendritic Molecules”, J. Am. Chem. Soc. (2008) 130, 10864–10865.

    Google Scholar 

  8. Sawama, Y.; Goto, R.; Nagata, S.; Shishido, Y.; Monguchi, Y.; Sajiki, H., “Chemoselective and Direct Functionalization of Methyl Benzyl Ethers and Unsymmetrical Dibenzyl Ethers by Using Iron Trichloride”, Chem. Eur. J. (2014) 20, 2631–2636.

    Google Scholar 

  9. Sawama, Y.; Masuda, M.; Asai, S.; Goto, R.; Nagata, S.; Nishimura, S.; Monguchi, Y.: Sajiki, H., “FeCl 3 -Catalyzed Self-Cleaving Deprotection of Methoxyphenylmethyl-Protected Alcohols”, Org. Lett. (2015) 17, 434–437.

    Google Scholar 

  10. Sawama, Y.; Masuda, M.; Honda, A.; Yokoyama, H.; Park, K.; Yasukawa, N.; Monguchi, Y.; Sajiki, H., “Additional Nucleophile-Free FeCl 3 -Catalyzed Green Deprotection of 2,4-Dimethoxyphenylmethyl-Protected Alcohols and Carboxylic acids”, Chem. Pharm. Bull. (2016) 64, 778–784.

    Google Scholar 

  11. Sawama, Y.; Sawama, Y.; Krause, N., “Highly Regioselective Gold-Catalyzed Ring-Opening Allylation and Azidation of Dihydrofurans”, Org. Lett. (2009) 11, 5034–5037.

    Google Scholar 

  12. Sawama, Y.; Shibata, K.; Sawama, Y.; Takubo, M.; Monguchi, Y.; Krause, N.; Sajiki, H., “Iron-Catalyzed Ring-Opening Azidation and Allylation of O-Heterocycles”, Org. Lett. (2013) 15, 5282–5285.

    Google Scholar 

  13. Sawama, Y.; Asai, S.; Kawajiri, T.; Monguchi, Y.; Sajiki, H., “Biaryl Synthesis by Ring-Opening Friedel-Crafts Arylation of 1,4-Epoxy-1,4-dihydronaphthalenes Catalyzed by Iron Trichloride”, Chem. Eur. J. (2015) 21, 2222–2229.

    Google Scholar 

  14. Sawama, Y.; Kawamoto, K.; Satake, H.; Krause, N.; Kita, Y., “Regioselective Gold-Catalyzed Allylative Ring-Opening of 1,4-Epoxy-1,4-dihydronaphthalenes”, Synlett (2010) 14, 2151–2155.

    Google Scholar 

  15. Sawama, Y.; Ogata, Y.; Kawamoto, K.; Satake, H.; Shibata, K.; Monguchi, Y.; Sajiki, H.; Kita, Y., “Lewis Acid-Catalyzed Ring-Opening Functionalizations of 1,4-Epoxy-1,4-dihydronaphthalenes”, Adv. Synth. Catal. (2013) 355, 517–528.

    Google Scholar 

  16. Rokita, S. E., “Quinone Methides”, Vol. 1, John Wiley & Sons Ltd, New Jersey, (2009).

    Google Scholar 

  17. Sawama, Y.; Shishido, Y.; Yanase, T.; Kawamoto, K.; Goto, R.; Monguchi, Y.; Sajiki, H., “Efficient Generation of ortho-Naphthoquinone Methides from 1,4-Epoxy-1,4-dihydronaphthalenes and Their Annulation with Allyl Silanes”, Angew. Chem. Int. Ed. (2013) 52, 1515–1519.

    Google Scholar 

  18. Sawama, Y.; Kawajiri, T.; Asai, S.; Yasukawa, N.; Shishido, Y.; Monguchi, Y.; Sajiki, H., “Biarylmethane and Fused Heterocyclic Arene Synthesis via in situ Generated o- and/or p-Naphthoquinone Methides”, J. Org. Chem. (2015) 80, 5556–5565.

    Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Yoshinari Sawama .

Editor information

Editors and Affiliations

Rights and permissions

Reprints and permissions

Copyright information

© 2017 Springer Nature Singapore Pte Ltd.

About this chapter

Cite this chapter

Sawama, Y. (2017). Environment-Friendly Iron-Catalyzed Reactions. In: Tomioka, K., Shioiri, T., Sajiki, H. (eds) New Horizons of Process Chemistry. Springer, Singapore. https://doi.org/10.1007/978-981-10-3421-3_5

Download citation

Publish with us

Policies and ethics