Skip to main content
SpringerLink
Log in

A facile access for the C-N bond formation by transition metal-free oxidative coupling of benzylic C-H bonds and amides

  • Articles
  • Published:
Science China Chemistry Aims and scope Submit manuscript

Abstract

Using 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) as the oxidant, we communicate an efficient oxidative C-N coupling of benzylic C-H bonds with amides to afford a series of amination products in good yields. A wide range of functional groups as well as various sulfonamides and carboxamides are well tolerated. Moreover, this reaction involves both the challenging C-H functionalization and C-N bond formation.

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

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. Correa A, Bolm C. Metal-catalyzed C(sp2)-N bond formation. In: Taillefer M, Ma D, Eds. Amination and Formation of sp 2 C-N. Vol. 46. Berlin Heidelberg: Springer, 2013. 55–85

    Google Scholar 

  2. Davies HML, Manning JR. Catalytic C-H functionalization by metal carbenoid and nitrenoid insertion. Nature, 2008, 451: 417–424

    Article  CAS  Google Scholar 

  3. Chiba S, Narasaka K. Simple Molecules, Highly Efficient Amination. Verlag GmbH & Co. KGaA: Wiley-VCH, 2008. 1–54

    Google Scholar 

  4. Dick AR, Sanford MS. Transition metal catalyzed oxidative functionalization of carbon-hydrogen bonds. Tetrahedron, 2006, 62: 2439–2463

    Article  CAS  Google Scholar 

  5. Davies HML. Recent advances in catalytic enantioselective intermolecular C-H functionalization. Angew Chem Int Ed, 2006, 45: 6422–6425

    Article  CAS  Google Scholar 

  6. Davies HML, Long MS. Recent advances in catalytic intramolecular C-H aminations. Angew Chem Int Ed, 2005, 44: 3518–3520

    Article  CAS  Google Scholar 

  7. Xie Y, Zhao Y, Qian B, Yang L, Xia C, Huang H. Enantioselective N-H functionalization of indoles with α,β-unsaturated γ-lactams catalyzed by chiral Brønsted acids. Angew Chem Int Ed, 2011, 50: 5682–5686

    Article  CAS  Google Scholar 

  8. Li ZP, Li CJ. A highly efficient cubr-catalyzed alkynylation of sp3 C-H bond. J Am Chem Soc, 2004, 126: 11810–11811

    Article  CAS  Google Scholar 

  9. Li CJ. Cross-dehydrogenative-coupling (CDC): explore C-C bond formations beyond functional group transformations. Acc Chem Res, 2009, 42: 335–344

    Article  CAS  Google Scholar 

  10. Collet F, Lescot C, Dauban P. Catalytic C-H amination: the stereoselectivity issue. Chem Soc Rev, 2011, 40: 1926–1936

    Article  CAS  Google Scholar 

  11. Collet F, Dodd RH, Dauban P. Catalytic C-H amination: recent progress and future directions. Chem Commun, 2009: 5061–5074

    Google Scholar 

  12. Breslow R, Gellman SH. Intramolecular nitrene carbon-hydrogen insertions mediated by transition-metal complexes as nitrogen analogs of cytochrome P-450 reactions. J Am Chem Soc, 1983, 105: 6728–6729

    Article  CAS  Google Scholar 

  13. Breslow R, Gellman SH. Tosylamidation of cyclohexane by a cytochrome P-450 model. J Chem Soc Chem Commun, 1982: 1400–1401

    Google Scholar 

  14. Kurokawa T, Kim M, Du Bois J. Synthesis of 1,3-diamines through rhodium-catalyzed C-H insertion. Angew Chem, Int Ed, 2009, 48: 2777–2779

    Article  CAS  Google Scholar 

  15. Fiori KW, Du Bois J. Catalytic intermolecular amination of C-H bonds: method development and mechanistic insights. J Am Chem Soc, 2007, 129: 562–568

    Article  CAS  Google Scholar 

  16. Espino CG, Wehn PM, Chow J, Du Bois J. Synthesis of 1,3-difunctionalized amine derivatives through selective C-H bond oxidation. J Am Chem Soc, 2001, 123: 6935–6936

    Article  CAS  Google Scholar 

  17. Nägeli I, Baud C, Bernardinelli G, Jacquier Y, Moraon M, Müllet P. Rhodium(II)-catalyzed CH insertions with {[(4-nitrophenyl)sulfonyl] imino}phenyl-λ3-iodane. Helv Chim Acta, 1997, 80: 1087–1105

    Article  Google Scholar 

  18. Leung SKY, Tsui WM, Huang JS, Che CM, Liang JL, Zhu N. Imido transfer from bis(imido)ruthenium(VI) porphyrins to hydrocarbons: effect of imido substituents, C-H bond dissociation energies, and RuVI/V reduction potentials. J Am Chem Soc, 2005, 127: 16629–16640

    Article  CAS  Google Scholar 

  19. Liang JL, Yuan SX, Huang JS, Yu WY, Che CM. Highly diastereo- and enantioselective intramolecular amidation of saturated C-H bonds catalyzed by ruthenium porphyrins. Angew Chem Int Ed, 2002, 41: 3465–3468

    Article  CAS  Google Scholar 

  20. Yu XQ, Huang JS, Zhou XG, Che CM. Amidation of saturated C-H bonds catalyzed by electron-deficient ruthenium and manganese porphyrins. A highly catalytic nitrogen atom transfer process. Org Lett, 2000, 2: 2233–2236

    CAS  Google Scholar 

  21. Wu Y, Wang J, Mao F, Kwong FY. Palladium-catalyzed cross-dehydrogenative functionalization of C(sp2)-H bonds. Chem-Asian J, 2014, 9: 26–47

    Article  CAS  Google Scholar 

  22. Banerjee D, Junge K, Beller M. Cooperative catalysis by palladium and a chiral phosphoric acid: enantioselective amination of racemic allylic alcohols. Angew Chem Int Ed, 2014, 53: 13049–13053

    Article  CAS  Google Scholar 

  23. Neumann JJ, Rakshit S, Dröge T, Glorius F. Palladium-catalyzed amidation of unactivated C(sp3)-H bonds: from anilines to indolines. Angew Chem Int Ed, 2009, 48: 6892–6895

    Article  CAS  Google Scholar 

  24. Thu HY, Yu WY, Che CM. Intermolecular amidation of unactivated sp2 and sp3 C-H bonds via palladium-catalyzed cascade C-H activation/nitrene insertion. J Am Chem Soc, 2006, 128: 9048–9049

    Article  CAS  Google Scholar 

  25. Hu J, Xie Y, Huang H. Palladium-catalyzed insertion of an allene into an aminal: aminomethylamination of allenes by C-N bond activation. Angew Chem Int Ed, 2014, 53: 7272–7276

    Article  CAS  Google Scholar 

  26. Priebbenow DL, Bolm C. C-H activation of methyl arenes in the MnO2-mediated aroylation of N-chlorosulfoximines. Org Lett, 2014, 16: 1650–1652

    Article  CAS  Google Scholar 

  27. Yi H, Liu Q, Liu J, Zeng Z, Yang Y, Lei A. DDQ-catalyzed oxidative C-O coupling of sp3 C-H bonds with carboxylic acids. Chem Sus Chem, 2012, 5: 2143–2146

    Article  CAS  Google Scholar 

  28. Kohmura Y, Katsuki T. Mn(salen)-catalyzed enantioselective C-H amination. Tetrahedron Lett, 2001, 42: 3339–3342

    Article  CAS  Google Scholar 

  29. Li Z, Capretto DA, Rahaman R, He C. Silver-catalyzed intermolecular amination of C-H groups. Angew Chem Int Ed, 2007, 46: 5184–5186

    Article  CAS  Google Scholar 

  30. Cui Y, He C. A silver-catalyzed intramolecular amidation of saturated C-H bonds. Angew Chem Int Ed, 2004, 43: 4210–4212

    Article  CAS  Google Scholar 

  31. Li Z, Capretto DA, Rahaman RO, He C. Gold(III)-catalyzed nitrene insertion into aromatic and benzylic C-H groups. J Am Chem Soc, 2007, 129: 12058–12059

    Article  CAS  Google Scholar 

  32. Wang L, Priebbenow DL, Dong W, Bolm C. N-arylations of sulfoximines with 2-arylpyridines by copper-mediated dual N-H/C-H activation. Org Lett, 2014, 16: 2661–2663

    Article  CAS  Google Scholar 

  33. Ni Z, Zhang Q, Xiong T, Zheng Y, Li Y, Zhang H, Zhang J, Liu Q. Highly regioselective copper-catalyzed benzylic C-H amination by N-fluorobenzenesulfonimide. Angew Chem Int Ed, 2012, 51: 1244–1247

    Article  CAS  Google Scholar 

  34. Liu X, Zhang Y, Wang L, Fu H, Jiang Y, Zhao Y. General and efficient copper-catalyzed amidation of saturated C-H bonds using N-halosuccinimides as the oxidants. J Org Chem, 2008, 73: 6207–6212

    Article  CAS  Google Scholar 

  35. He L, Yu J, Zhang J, Yu X-Q. α-Amidation of cyclic ethers catalyzed by simple copper salt and a mild and efficient preparation method for α, ϖ-amino alcohols. Org Lett, 2007, 9: 2277–2280

    Article  CAS  Google Scholar 

  36. Bhuyan R, Nicholas KM. Efficient copper-catalyzed benzylic amidation with anhydrous chloramine-T. Org Lett, 2007, 9: 3957–3959

    Article  CAS  Google Scholar 

  37. Pelletier G, Powell DA. Copper-catalyzed amidation of allylic and benzylic C-H bonds. Org Lett, 2006, 8: 6031–6034

    Article  CAS  Google Scholar 

  38. Fructos MR, Trofimenko S, Díaz-Requejo MM, Pérez PJ. Facile amine formation by intermolecular catalytic amidation of carbon-hydrogen bonds. J Am Chem Soc, 2006, 128: 11784–11791

    Article  CAS  Google Scholar 

  39. Li X, Liu X, Chen H, Wu W, Qi C, Jiang H. Copper-catalyzed aerobic oxidative transformation of ketone-derived N-tosyl hydrazones: an entry to alkynes. Angew Chem Int Ed, 2014, 53: 14485–14489

    Article  CAS  Google Scholar 

  40. Ye Y-H, Zhang J, Wang G, Chen SY, Yu XQ. Cobalt-catalyzed benzylic C-H amination via dehydrogenative-coupling reaction. Tetrahedron, 2011, 67: 4649–4654

    Article  CAS  Google Scholar 

  41. Harden JD, Ruppel JV, Gao GY, Zhang XP. Cobalt-catalyzed intermolecular C-H amination with bromamine-T as nitrene source. Chem Commun, 2007, 0: 4644–4646

    Article  CAS  Google Scholar 

  42. Ragaini F, Penoni A, Gallo E, Tollari S, Li Gotti C, Lapadula M, Mangioni E, Cenini S. Amination of benzylic C-H bonds by arylazides catalyzed by Co(II)-porphyrin complexes: a synthetic and mechanistic study. Chem Eur J, 2003, 9: 249–259

    Article  CAS  Google Scholar 

  43. Cheng Y, Dong W, Wang L, Parthasarathy K, Bolm C. Iron-catalyzed hetero-cross-dehydrogenative coupling reactions of sulfox-imines with diarylmethanes: a new route to N-alkylated sulfoximines. Org Lett, 2014, 16: 2000–2002

    Article  CAS  Google Scholar 

  44. Wang Z, Zhang Y, Fu H, Jiang Y, Zhao Y. Efficient intermolecular iron-catalyzed amidation of C-H bonds in the presence of N-bromosuccinimide. Org Lett, 2008, 10: 1863–1866

    Article  CAS  Google Scholar 

  45. Chan TL, Wu Y, Choy PY, Kwong FY. A radical process towards the development of transition-metal-free aromatic carbon-carbon bondforming reactions. Chem Eur J, 2013, 19: 15802–15814

    Article  CAS  Google Scholar 

  46. Truong T, Daugulis O. Base-mediated intermolecular sp2 C-H bond arylation via benzyne intermediates. J Am Chem Soc, 2011, 133: 4243–4245

    Article  CAS  Google Scholar 

  47. Sun CL, Li H, Yu DG, Yu M, Zhou X, Lu XY, Huang K, Zheng SF, Li BJ, Shi ZJ. An efficient organocatalytic method for constructing biaryls through aromatic C-H activation. Nat Chem, 2010, 2: 1044–1049

    Article  CAS  Google Scholar 

  48. Shirakawa E, Itoh K-I, Higashino T, Hayashi T. tert-Butoxide-mediated arylation of benzene with aryl halides in the presence of a catalytic 1,10-phenanthroline derivative. J Am Chem Soc, 2010, 132: 15537–15539

    Article  CAS  Google Scholar 

  49. Liu W, Cao H, Zhang H, Zhang H, Chung KH, He C, Wang H, Kwong FY, Lei A. Organocatalysis in cross-coupling: DMEDA-catalyzed direct C-H arylation of unactivated benzene. J Am Chem Soc, 2010, 132: 16737–16740

    Article  CAS  Google Scholar 

  50. Yanagisawa S, Ueda K, Taniguchi T, Itami K. Potassium t-butoxide alone can promote the biaryl coupling of electron-deficient nitrogen heterocycles and haloarenes. Org Lett, 2008, 10: 4673–4676

    Article  CAS  Google Scholar 

  51. Ochiai M, Miyamoto K, Kaneaki T, Hayashi S, Nakanishi W. Highly regioselective amination of unactivated alkanes by hypervalent sulfonylimino-λ3-bromane. Science, 2011, 332: 448–451

    Article  CAS  Google Scholar 

  52. Kim HJ, Kim J, Cho SH, Chang S. Intermolecular oxidative C-N bond formation under metal-free conditions: control of chemoselectivity between aryl sp2 and benzylic sp3 C-H bond imidation. J Am Chem Soc, 2011, 133: 16382–16385

    Article  CAS  Google Scholar 

  53. Fan R, Li W, Pu D, Zhang L. Transition-metal-free intermolecular amination of sp3 C-H bonds with sulfonamides. Org Lett, 2009, 11: 1425–1428

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, 430072, China

    Jie Liu, Heng Zhang, Hong Yi, Chao Liu & Aiwen Lei

  2. National Research Centre for Carbohydrate Synthesis, Jiangxi Normal University, Nanchang, 330022, China

    Aiwen Lei

Authors
  1. Jie Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Heng Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Hong Yi
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Chao Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Aiwen Lei
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding authors

Correspondence to Chao Liu or Aiwen Lei.

Electronic supplementary material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Liu, J., Zhang, H., Yi, H. et al. A facile access for the C-N bond formation by transition metal-free oxidative coupling of benzylic C-H bonds and amides. Sci. China Chem. 58, 1323–1328 (2015). https://doi.org/10.1007/s11426-015-5381-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11426-015-5381-2

Keywords

Search

Navigation