Skip to main content
SpringerLink
Log in
Book cover

Functionalization of Carborane via Carboryne Intermediates pp 117–126Cite as

Cage Boron Arylation of o-Carborane via Metal-Free, Visible-Light-Mediated Radical Coupling

  • Chapter
  • First Online:

  • 331 Accesses

Part of the book series: Springer Theses ((Springer Theses))

Abstract

This chapter demonstrates that 3-diazonium-o-carborane tetrafluoroborate can serve as not only an efficient precursor for 1,3-dehydro-o-carborane, but also an ideal source of o-carboranyl boryl radical in the presence of visible light. For instance, the resulting o-carboranyl boryl radical can undergo regioselective C–H insertion reaction with simple arenes bearing a wide range of functional groups. This general and simple procedure provides a transition-metal-free alternative for the synthesis of cage boron-arylated o-carboranes, which may found application in materials science. This work also represents a synthetic useful application of boryl radicals.

This is a preview of subscription content, 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   84.99
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD   109.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD   109.99
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. (a) Jones W, Feher, F (1989) Comparative reactivities of hydrocarbon carbon-hydrogen bonds with a transition-metal complex. Acc Chem Res 22(3):91–100 (b) Labinger JA, Bercaw JE (2002) Understanding and exploiting C–H bond activation. Nature 417(6888):507–514 (c) Dyker G (2005) Handbook of C–H transformations: Applications in organic synthesis. Wiley-VCH, Weinheim (d) Godula K, Sames D (2006) C–H bond functionalization in complex organic synthesis. Science 312(5770):67–72 (e) Bergman RG (2007) Organometallic chemistry: C–H activation. Nature 446(7134):391–393

    Google Scholar 

  2. (a) Narayanam JMR, Stephenson CRJ (2011) Visible light photoredox catalysis: Applications in organic synthesis. Chem Soc Rev 40(1):102–113 (b) Prier CK, Rankic DA, MacMillan DWC (2013) Visible light photoredox catalysis with transition metal complexes: Applications in organic synthesis. Chem Rev 113(7):5322–5363 (c) Schultz DM, Yoon TP (2014) Solar synthesis: Prospects in visible light photocatalysis. Science 343(6174):985

    Google Scholar 

  3. (a) Kracke GR, VanGordon MR, Sevryugina YV et al (2015) Carborane-derived local anesthetics are isomer dependent. Chemmedchem 10(1):62–67 (b) Wilkinson SM, Gunosewoyo H, Barron ML et al (2014) The first cns-active carborane: A novel P2X7 receptor antagonist with antidepressant activity. Acs Chem Neurosci 5(5):335–339 (c) Scholz M, Kaluderovic GN, Kommera H et al (2011) Carbaboranes as pharmacophores: Similarities and differences between aspirin and asborin. Eur J Med Chem 46(4):1131–1139 (d) Beer ML, Lemon J, Valliant JF (2010) Preparation and evaluation of carborane analogues of tamoxifen. J Med Chem 53(22):8012–8020 (e) Julius RL, Farha OK, Chiang J et al (2007) Synthesis and evaluation of transthyretin amyloidosis inhibitors containing carborane pharmacophores. Proc Natl Acad Sci USA 104(12):4808–4813

    Google Scholar 

  4. (a) Visbal R, Ospino I, Lopez-de-Luzuriaga JM et al (2013) N-heterocyclic carbene ligands as modulators of luminescence in three-coordinate gold (I) complexes with spectacular quantum yields. J Am Chem Soc 135(12):4712–4715 (b) Cioran AM, Musteti AD, Teixidor F et al (2012) Mercaptocarborane-capped gold nanoparticles: Electron pools and ion traps with switchable hydrophilicity. J Am Chem Soc 134(1):212–221 (c) Koshino M, Tanaka T, Solin N et al (2007) Imaging of single organic molecules in motion. Science 316(5826):853–853 (d) Yinghuai Z, Peng AT, Carpenter K et al (2005) Substituted carborane-appended water-soluble single-wall carbon nanotubes: New approach to boron neutron capture therapy drug delivery. J Am Chem Soc 127(27):9875–9880

    Google Scholar 

  5. (a) Hosmane NS, Maguire JA (2007) d- and f-Block metallacarbaboranes in Crabtree RH, Mingos DMP (eds) Comprehensive Organometallic Chemistry III, Elsevier, Oxford (b) Xie Z (2002) Advances in the chemistry of metallacarboranes of f-block elements. Coord Chem Rev 231(1–2):23–46 (c) Xie Z (2003) Cyclopentadienyl-carboranyl hybrid compounds: a new class of versatile ligands for organometallic chemistry. 36(1):1–9 (d) Deng L, Xie Z (2007) Advances in the chemistry of carboranes and metallacarboranes with more than 12 vertices. Coord Chem Rev 251(17–20):2452–2476 (e) Yao ZJ, Jin GX (2013) Transition metal complexes based on carboranyl ligands containing N, P, and S donors: Synthesis, reactivity and applications. Coordin Chem Rev 257(17–18):2522–2535 (f) Zhang J, Xie Z (2014) Synthesis, structure, and reactivity of 13- and 14-vertex carboranes. Acc Chem Res 47(5):1623–1633

    Google Scholar 

  6. (a) Wee KR, Han WS, Cho DW et al (2012) Carborane photochemistry triggered by aryl substitution: Carborane-based dyads with phenyl carbazoles. Angew Chem Int Ed 51(11):2677–2680 (b) Wee KR, Cho YJ, Song JK et al (2013) Multiple photoluminescence from 1,2-dinaphthyl-ortho-carborane. Angew Chem Int Ed 52(37):9682–9685 (c) Wee KR, Cho YJ, Jeong S et al (2012) Carborane-based optoelectronically active organic molecules: Wide band gap host materials for blue phosphorescence. J Am Chem Soc 134(43):17982–17990

    Google Scholar 

  7. (a) Wee KR, Han WS, Cho DW et al (2012) Carborane photochemistry triggered by aryl substitution: Carborane-based dyads with phenyl carbazoles. Angew Chem Int Ed 51(11):2677–2680 (b) Wee KR, Cho YJ, Jeong S et al (2012) Carborane-based optoelectronically active organic molecules: Wide band gap host materials for blue phosphorescence. J Am Chem Soc 134(43):17982–17990 (c) Ferrer-Ugalde A, Juarez-Perez EJ, Teixidor F et al (2012) Synthesis and characterization of new fluorescent styrene-containing carborane derivatives: The singular quenching role of a phenyl substituent. Chem-Eur J 18(2):544–553 (d) Wee KR, Cho YJ, Song JK et al (2013) Multiple photoluminescence from 1,2-dinaphthyl-ortho-carborane. Angew Chem Int Ed 52(37):9682–9685 (e) Shi C, Sun HB, Tang X et al (2013) Variable photophysical properties of phosphorescent iridium(iii) complexes triggered by closo- and nido-carborane substitution. Angew Chem Int Ed 52(50):13434–13438 (f) Shi C, Sun HB, Jiang QB et al (2013) Carborane tuning of photophysical properties of phosphorescent iridium (iii) complexes. Chem Commun 49 (42):4746–4748 (g) Bae HJ, Chung J, Kim H et al (2014) Deep red phosphorescence of cyclometalated iridium complexes by o-carborane substitution. Inorg Chem 53(1):128–138 (h) Naito H, Morisaki Y, Chujo Y (2015) o-Carborane-based anthracene: A variety of emission behaviors. Angew Chem Int Ed 54(17):5084–5087 (i) Ferrer-Ugalde A, Gonzalez-Campo A, Vinas C et al (2014) Fluorescence of new o-carborane compounds with different fluorophores: Can it be tuned? Chem-Eur J 20(32):9940–9951 (j) Tang C, Xie Z (2015) Nickel-catalyzed cross-coupling reactions of o-carboranyl with aryl iodides: Facile synthesis of 1-aryl-o-carboranes and 1,2-diaryl-o-carboranes. Angew Chem Int Ed 54(26):7662–7665

    Google Scholar 

  8. (a) Vinas C, Barbera G, Oliva JM et al (2001) Are halocarboranes suitable for substitution reactions? The case for 3-I-1,2-closo- C2B10H11: Molecular orbital calculations, aryldehalogenation reactions, 11B NMR interpretation of closo-carboranes, and molecular structures of 1-Ph-3-Br-1,2-closo- C2B10H10 and 3-Ph-1,2-closo-C2B10H11. Inorg Chem 40(26):6555–6562 (b) Aizawa K, Ohta K, Endo Y (2010) Synthesis of 3-aryl-1,2-dicarba-closo-dodecaboranes by suzuki-miyaura coupling reaction. Heterocycles 80(1):369–377 (c) Jin GF, Hwang JH, Lee JD et al (2013) A three-dimensional pi-electron acceptor, tri-phenyl-o-carborane, bearing a rigid conformation with end-on phenyl units. Chem Commun 49 (82):9398–9400 (d) Barbera G, Vaca A, Teixidor F et al (2008) Designed synthesis of new ortho-carborane derivatives: From mono- to polysubstituted frameworks. Inorg Chem 47(16):7309–7316 (e) Ohta K, Yamazaki H, Endo Y (2009) Magnesium-assisted intramolecular demethylation utilizing carborane C-H geometry. J Organomet Chem 694 (11):1646–1651 (f) Eriksson L, Beletskaya IP, Bregadze VI et al (2002) Palladium-catalyzed cross-coupling reactions of arylboronic acids and 2-i-p-carborane. J Organomet Chem 657(1–2):267–272 (g) Hawthorn.Mf, Wegner PA (1968) Reconstruction of 1,2-dicarbaclovododecaborane(12) structure by boron-atom insertion with (3)-1,2-dicarbollide ions. J Am Chem Soc 90(4):896–901. (h) Roscoe JS, Kongpric.S, Papetti S (1970) Icosahedral carboranes .14. Preparation of boron-substituted carboranes by boron-insertion reaction. Inorg Chem 9 (6):1561–1563. (i) Ogawa T, Ohta K, Yoshimi T et al (2006) M-carborane bisphenol structure as a pharmacophore for selective estrogen receptor modulators. Bioorg Med Chem Lett 16(15):3943–3946 (j) Safronov AV, Shlyakhtina NI, Hawthorne MF (2012) New approach to the synthesis of 3-alkyl-1,2-dicarba-closo-dodecaboranes: Reaction of alkyldichloroboranes with thallium dicarbollide. Organometallics 31(7):2764–2769 (k) Quan YJ, Xie ZW (2015) Palladium-catalyzed regioselective intramolecular coupling of o-carborane with aromatics via direct cage b-h activation. J Am Chem Soc 137(10):3502–3505 (l) Cao K, Huang YW, Yang JX et al (2015) Palladium catalyzed selective mono-arylation of o-carboranes via B-H activation. Chem Commun 51(33):7257–7260

    Google Scholar 

  9. Beletskaya IP, Bregadze VI, Kabytaev KZ et al (2007) Palladium-catalyzed amination of 2-iodo-para-carborane. Organometallics 26(9):2340–2347

    Google Scholar 

  10. Vondrak T, Plesek J, Hermanek S et al (1989) Charge-distribution in icosahedral carboranes: a UV photoelectron spectroscopic study. Polyhedron 8(6):805–811

    Google Scholar 

  11. Zhao D, Zhang J, Xie Z (2014) 1,3-dehydro-o-carborane: Generation and reaction with arenes. Angew Chem Int Ed 53(32):8488–8491

    Google Scholar 

  12. (a) Mo FY, Dong GB, Zhang Y et al (2013) Recent applications of arene diazonium salts in organic synthesis. Org Biomol Chem 11(10):1582–1593 (b) Hari DP, Konig B (2013) The photocatalyzed meerwein arylation: Classic reaction of aryl diazonium salts in a new light. Angew Chem Int Edit 52(18):4734–4743 (c) Ando, W (2010) Diazonium and Diazo Groups. Wiley, Chichester (d) Mahouche-Chergui S, Gam-Derouich S, Mangeney C et al (2011) Aryl diazonium salts: A new class of coupling agents for bonding polymers, biomacromolecules and nanoparticles to surfaces. Chem Soc Rev 40(7):4143–4166 (e) Roglans A, Pla-Quintana A, Moreno-Manas M (2006) Diazonium salts as substrates in palladium-catalyzed cross-coupling reactions. Chem Rev 106(11):4622–4643 (f) Felpin FX, Nassar-Hardy L, Le Callonnec F et al (2011) Recent advances in the heck-matsuda reaction in heterocyclic chemistry. Tetrahedron 67(16):2815–2831 (g) Taylor JG, Moro AV, Correia CRD (2011) Evolution and synthetic applications of the heck-matsuda reaction: The return of arenediazonium salts to prominence. Eur J Org Chem (8):1403–1428

    Google Scholar 

  13. (a) Kalyani D, McMurtrey KB, Neufeldt SR et al (2011) Room-temperature C-H arylation: Merger of pd-catalyzed c-h functionalization and visible-light photocatalysis. J Am Chem Soc 133(46):18566–18569 (b) Hari DP, Schroll P, Konig B (2012) Metal-free, visible-light-mediated direct C-H arylation of heteroarenes with aryl diazonium salts. J Am Chem Soc 134(6):2958–2961 (c) Heinrich MR, Wetzel A, Kirschstein M (2007) Intermolecular radical carboaminohydroxylation of olefins with aryl diazonium salts and tempo. Org Lett 9 (19):3833–3835 (d) Pratsch G, Anger CA, Ritter K et al (2011) Hydroxy- and aminophenyl radicals from arenediazonium salts. Chem-Eur J 17(15):4104–4108 (e) Wetzel A, Ehrhardt V, Heinrich MR (2008) Synthesis of amino- and hydroxybiphenyls by radical chain reaction of arenediazonium salts. Angew Chem Int Ed 47(47):9130–9133 (f) Wetzel A, Pratsch G, Kolb R et al (2010) Radical arylation of phenols, phenyl ethers, and furans. Chem-Eur J 16(8):2547–2556 (g) Lazarides T, McCormick T, Du PW et al (2009) Making hydrogen from water using a homogeneous system without noble metals. J Am Chem Soc 131(26):9192–9194 (h) Liu HJ, Feng W, Kee CW et al (2010) Organic dye photocatalyzed alpha-oxyamination through irradiation with visible light. Green Chem 12(6):953–956 (i) ari DP, Hering T, Konig B (2012) Visible light photocatalytic synthesis of benzothiophenes. Org Lett 14(20):5334–5337 (j) Hartmann M, Li Y, Studer A (2012) Transition-metal-free oxyarylation of alkenes with aryl diazonium salts and tempona. J Am Chem Soc 134(40):16516–16519 (k) Ding YY, Cheng K, Qi CZ et al (2012) Ferrous salt-promoted homocoupling of arenediazonium tetrafluoroborates under mild conditions. Tetrahedron Lett 53(46):6269–6272

    Google Scholar 

  14. (a) Curran DP, Solovyev A, Brahmi MM et al (2011) Synthesis and reactions of n-heterocyclic carbene boranes. Angew Chem Int Ed 50(44):10294–10317 (b) Martin CD, Soleilhavoup M, Bertrand G (2013) Carbene-stabilized main group radicals and radical ions. Chem Sci 4(8):3020–3030 (c) Lu DM, Wu C, Li PF (2014) Synergistic effects of lewis bases and substituents on the electronic structure and reactivity of boryl radicals. Chem-Eur J 20(6):1630–1637 (d) Ueng SH, Fensterbank L, Lacote E et al (2010) Radical deoxygenation of xanthates and related functional groups with new minimalist n-heterocyclic carbene boranes. Org Lett 12(13):3002–3005 (e) Pan XC, Lacote E, Lalevee J et al (2012) Polarity reversal catalysis in radical reductions of halides by n-heterocyclic carbene boranes. J Am Chem Soc 134(12):5669–5674 (f) Pan XC, Vallet AL, Schweizer S et al (2013) Mechanistic and preparative studies of radical chain homolytic substitution reactions of n-heterocyclic carbene boranes and disulfides. J Am Chem Soc 135(28):1048410491

    Google Scholar 

  15. Zakharkin LI, Kovredov AI, Olshevskaya VA et al (1984) Synthesis of sigma-(ortho-carboran-9-yl)- and sigma-(meta-carboran-9-yl)-pi-cyclopentadienyldicarbonyliron and their rearrangement in reactions with bromine to pi-(ortho-carboran-9-yl)cyclopentadienyl and pi-(meta-carboran-9-yl)cyclopentadienyl-dicarbonyliron bromides, respectively. J Organomet Chem 267(1):81–91

    Google Scholar 

  16. Zharov I, Havlas Z, Orendt AM et al (2006) CB11Me11 boronium ylides: Carba-closo-dodecaboranes with a naked boron vertex. J Am Chem Soc 128(18):6089–6100

    Google Scholar 

  17. Ringstrand B, Kaszynski P (2013) Functionalization of the [closo-1-CB9H10]− anion for the construction of new classes of liquid crystals. Acc Chem Res 46(2):214–225

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong, Hong Kong, China

    Da Zhao

Authors
  1. Da Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Da Zhao .

Rights and permissions

Reprints and permissions

Copyright information

© 2016 Springer Science+Business Media Singapore

About this chapter

Cite this chapter

Zhao, D. (2016). Cage Boron Arylation of o-Carborane via Metal-Free, Visible-Light-Mediated Radical Coupling. In: Functionalization of Carborane via Carboryne Intermediates. Springer Theses. Springer, Singapore. https://doi.org/10.1007/978-981-10-1569-4_7

Download citation

Publish with us

Policies and ethics

Search

Navigation