Skip to main content
SpringerLink
Log in

Efficient Synthesis of Polycyclic Aromatic Hydrocarbons Using Unreactive Bonds

  • Chapter
  • First Online:
Middle Molecular Strategy

Abstract

The efficient, short-step synthesis of substituted polycyclic aromatic hydrocarbons (PAHs) via the ruthenium-catalyzed arylation reactions of C–H and C–O bonds in aromatic ketones with (hetero)arylboronates were described in this chapter. The C–H arylation of anthraquinone with arylboronates using RuH2(CO)(PPh3)3 as a catalyst gave 1,4,5,8-tetraarylanthraquinones, and then, it was converted to multiarylanthracenes by transformations of the carbonyl groups. Dibenzo[a,h]anthracenes and picenes were synthesized by utilizing the coupling reaction of acetophenones with (hetero)aryldiboronates and transformations of the acetyl groups. Sequential functionalization of the carbonyl group, that is, methylenation and dehydrogenative cyclization, in tetraarylanthraquinones gave 3,6,14,16-tetrasubstituted-tetrabenzo[a,d,j,m]coronenes. The stepwise ruthenium-catalyzed C–O and C–H arylation reactions of 1,4-dimethoxyanthraquinone gave tetraarylanthraquinones possessing two different aryl groups. These anthraquinones were converted to the 3,6,13,16-tetrasubstituted-tetrabenzo[a,d,j,m]coronenes having different substituents by the same carbonyl group transformations. Dibenzo[h,rst]pentaphenes and dibenzo[fg,qr]pentacenes were synthesized by combining the ruthenium-catalyzed chemoselective C–O arylation of 1,4- and 1,5-dimethoxyanthraquinones, Corey-Chaykofsky reaction, and Lewis acid-catalyzed dehydrative aromatization.

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

Access this chapter

Log in via an institution
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

Institutional subscriptions

References

  1. Wang C, Dong H, Hu W, Liu Y, Zhu D (2012) Semiconducting π-conjugated systems in field-effect transistors: a material odyssey of organic electronics. Chem Rev 112:2208–2267. https://doi.org/10.1021/cr100380z

    Article  CAS  PubMed  Google Scholar 

  2. Grimsdale AC, Chan LK, Martin RE, Jokisz PG, Holmes AB (2009) Synthesis of light-emitting conjugated polymers for applications in electroluminescent devices. Chem Rev 109:897–1091. https://doi.org/10.1021/cr000013v

    Article  CAS  PubMed  Google Scholar 

  3. Zhang X, Jiang X, Zhang K, Mao L, Luo J, Chi C, Chan HSO, Wu J (2010) Synthesis, self-assembly, and charge transporting property of contorted tetrabenzocoronenes. J Org Chem 75:8069–8077. https://doi.org/10.1021/jo101701k

    Article  CAS  PubMed  Google Scholar 

  4. Lee JCH, Hall DG (2014) State‐of‐the‐art in metal‐catalyzed cross‐coupling reactions of  organoboron compounds with organic electrophiles. In: de Meijere A, Bräse S, Oestreich M (eds) Metal-catalyzed cross-coupling reactions and more, Wiley, Weinheim, Germany, pp 65–132. https://doi.org/10.1002/9783527655588.ch2

  5. Hagui W, Doucet H, Soulé J-F (2019) Application of palladium-catalyzed C(sp2)–H bond arylation to the synthesis of polycyclic (hetero)aromatic. Chem 5:2006–2078. https://doi.org/10.1016/j.chempr.2019.06.005

    Article  CAS  Google Scholar 

  6. Kakiuchi F, Kan S, Igi K, Chatani N, Murai S (2003) A ruthenium-catalyzed reaction of aromatic ketones with arylboronates: A new method for the arylation of aromatic compounds via C–H bond cleavage. J Am Chem Soc 125:1698–1699. https://doi.org/10.1021/ja029273f

    Article  CAS  PubMed  Google Scholar 

  7. Kakiuchi F, Matsuura Y, Kan S, Chatani N (2005) A RuH2(CO)(PPh3)3-catalyzed regioselective arylation of aromatic ketones with arylboronates via carbon-hydrogen bond cleavage. J Am Chem Soc 127:5936–5945. https://doi.org/10.1021/ja043334n

    Article  CAS  PubMed  Google Scholar 

  8. Ueno S, Chatani N, Kakiuchi F (2007) Ruthenium-catalyzed carbon-carbon bond formation via the cleavage of an unreactive aryl carbon-nitrogen bond in aniline derivatives with organoboronates. J Am Chem Soc 129:6098–6099. https://doi.org/10.1021/ja0713431

    Article  CAS  PubMed  Google Scholar 

  9. Kakiuchi F, Usui M, Ueno S, Chatani N, Murai S (2004) Ruthenium-catalyzed functionalization of aryl carbon-oxygen bonds in aromatic ethers with organoboron compound. J Am Chem Soc 126:2706–2707. https://doi.org/10.1021/ja0393170

    Article  CAS  PubMed  Google Scholar 

  10. Ueno S, Mizushima E, Chatani N, Kakiuchi F (2006) Direct observation of the oxidative addition of the aryl carbon-oxygen bond to a ruthenium complex and consideration of the relative reactivity between aryl carbon-oxygen and aryl carbon-hydrogen bonds. J Am Chem Soc 128:16516–16517. https://doi.org/10.1021/ja067612p

    Article  CAS  PubMed  Google Scholar 

  11. Kondo H, Akiba N, Kochi T, Kakiuchi F (2015) Ruthenium-catalyzed monoalkenylation of aromatic ketones by cleavage of carbon-heteratom bonds with unconventional chemoselectivity. Angew Chem Int Ed 54:9293-9297. https://doi.org/10.1002/anie.201503641

    Article  CAS  Google Scholar 

  12. Kondo H, Kochi T, Kakiuchi F (2020) In situ generation of ruthenium carbonyl phosphine complexes as a versatile method for the development of enantioselective C–O bond arylation. Chem Eur J 26:1737–1741. https://doi.org/10.1002/chem.201905157

    Article  CAS  PubMed  Google Scholar 

  13. Kawamoto K, Kochi T, Sato M, Mizushima E, Kakiuchi F (2011) Ruthenium-catalyzed arylation of fluorinated aromatic ketones via ortho-selective carbon-fluorine bond cleavage. Tetrahedron Lett 52:5888–5890. https://doi.org/10.1016/j.tetlet.2011.09.005

    Article  CAS  Google Scholar 

  14. Ueno S, Kochi T, Chatani N, Kakiuchi F (2009) Unique effect of coordination of an alkene moiety in products on ruthenium-catalyzed chemoselective C–H alkenylation. Org Lett 11:855–858. https://doi.org/10.1021/ol802819b

    Article  CAS  PubMed  Google Scholar 

  15. Kitazawa K, Kochi T, Sato M, Kakiuchi F (2009) Convenient synthesis of tetra- and hexaarylanthracenes by means of RuH2(CO)(PPh3)3-catalyzed C–H arylation of anthraquinone with arylboronates. Org Lett 11:1951–1954. https://doi.org/10.1021/ol900393x

    Article  CAS  PubMed  Google Scholar 

  16. Izumoto A, Kondo H, Kochi T, Kakiuchi F (2017) Synthesis of fluorine-containing tetraarylanthracenes via ruthenium-catalyzed C–O or C–F arylation and their crystal structures. Synlett 28:2609–2613. https://doi.org/10.1055/s-0036-1590937

    Article  CAS  Google Scholar 

  17. Kitazawa K, Kochi T, Nitani M, Ie Y, Aso Y, Kakiuchi F (2011) Convenient synthesis of dibenzo[a, h]anthracenes and picenes via C–H arylation of acetophenones with arenediboronates. Chem Lett 40:300–302. https://doi.org/10.1246/cl.2011.300

    Article  CAS  Google Scholar 

  18. Terai S, Sato Y, Kochi T, Kakiuchi F (2020) Efficient synthesis of 3,6,13,16-tetrasubstituted-tetrabenzo[a, d, j, m]coronenes by selective C–H/C–O arylations of anthraquinone derivatives. Beilstein J Org Chem 16:544–550. https://doi.org/10.3762/bjoc.16.51

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  19. Suzuki Y, Yamada K, Watanabe K, Kochi T, Ie Y, Aso Y, Kakiuchi F (2017) Synthesis of dibenzo[h, rst]pentaphenes and dibenzo[fg, qr]pentacenes by the chemoselective C–O arylation of dimethoxyanthraquinones. Org Lett 19:3791–3794. https://doi.org/10.1021/acs.orglett.7b01666

    Article  CAS  PubMed  Google Scholar 

  20. Kondo H, Kochi T, Kakiuchi F (2017) Selective monoarylation of aromatic ketones and esters via cleavage of aromatic carbon—heteroatom bonds by trialkylphosphine ruthenium catalysts. Org Lett 19:794–797. https://doi.org/10.1021/acs.orglett.6b03761

    Article  CAS  PubMed  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, Faculty of Science and Technology, Keio University, Yokohama, Japan

    Fumitoshi Kakiuchi

Authors
  1. Fumitoshi Kakiuchi
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Fumitoshi Kakiuchi .

Editor information

Editors and Affiliations

  1. Graduate School of Science, Osaka University, Toyanaka, Osaka, Japan

    Koichi Fukase

  2. Graduate School of Pharmaceutical Sciences, Tohoku University, Sendai, Japan

    Takayuki Doi

Rights and permissions

Reprints and permissions

Copyright information

© 2021 The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd.

About this chapter

Check for updates. Verify currency and authenticity via CrossMark

Cite this chapter

Kakiuchi, F. (2021). Efficient Synthesis of Polycyclic Aromatic Hydrocarbons Using Unreactive Bonds. In: Fukase, K., Doi, T. (eds) Middle Molecular Strategy. Springer, Singapore. https://doi.org/10.1007/978-981-16-2458-2_11

Download citation

Publish with us

Policies and ethics

Search

Navigation