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Synlett 2011(4): 569-572  
DOI: 10.1055/s-0030-1259520
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

A Dehydrogenative Homocoupling Reaction for the Direct Synthesis of Hydrazines from N-Alkylanilines in Air

Xue-Ming Yana,c, Zhi-Ming Chena, Fei Yanga, Zhi-Zhen Huang*a,b
a College of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, P. R. of China
b Key Laboratory of Elemento-organic Chemistry, Nankai University, Tianjin 300071, P. R. of China
Fax: +86(025)83686231; e-Mail: huangzz@nju.edu.cn;
c College of Chemistry and Chemical Engineering, University of South China, Hengyang, Hunan 421001, P. R. of China
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Publication History

Received 1 December 2010
Publication Date:
27 January 2011 (online)

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Abstract

A copper-catalyzed N-N bond-forming reaction was performed by a dehydrogenative homocoupling of N-alkylanilines, affording N,N′-dialkyl-N,N′-diphenylhydrazines in 72-88% yields. This new strategy has the advantages of direct synthesis from N-alkylanilines, using air as the oxidant, convenient manipulations, mild reaction conditions and moderate to good yields. A possible mechanism by coordination and reductive elimination has been proposed.

Key words

homocoupling - oxidative dehydrogenation - copper catalyst - direct synthesis - hydrazine

    References and Notes

  • For recent reviews on oxidative cross-dehydrogenative-coupling, see:
  • 1a Li C.-J. Acc. Chem. Res.  2009,  42:  335 
    Search in Google Scholar
  • 1b Scheuermann CJ. Chem. Asian J.  2010,  5:  436 
    Search in Google Scholar
  • 1c Zhang M. Adv. Synth. Catal.  2009,  351:  2243 
    Search in Google Scholar
  • For representative papers on oxidative dehydrogenative homocouplings for the formation of C-C bonds, see:
  • 2a Truong T. Alvarado J. Tran LD. Daugulis O. Org. Lett.  2010,  12:  1200 
    Search in Google Scholar
  • 2b Chen Q.-A. Dong X. Chen M.-W. Wang D.-S. Zhou Y.-G. Li Y.-X. Org. Lett.  2010,  12:  1928 
    Search in Google Scholar
  • 2c Egami H. Katsuki T. J. Am. Chem. Soc.  2009,  131:  6082 
    Search in Google Scholar
  • 2d Hull KL. Lanni EL. Sanford MS.
    J. Am. Chem. Soc.  2006,  128:  14047 
    Search in Google Scholar
  • 2e Matsushita M. Kamata K. Yamaguchi K. Mizuno N. J. Am. Chem. Soc.  2005,  127:  6632 
    Search in Google Scholar
  • 2f Masui K. Ikegami H. Mori A. J. Am. Chem. Soc.  2004,  126:  5074 
    Search in Google Scholar
  • 2g Takahashi M. Masui K. Sekiguchi H. Kobayashi N. Mori A. Funahashi M. Tamaoki N. J. Am. Chem. Soc.  2006,  128:  10930 
    Search in Google Scholar
  • 2h Kamata K. Yamaguchi S. Kotani M. Yamaguchi K. Mizuno N. Angew. Chem. Int. Ed.  2008,  47:  2407 
    Search in Google Scholar
  • 2i Oi S. Sato H. Sugawara S. Inoue Y. Org. Lett.  2008,  10:  1823 
    Search in Google Scholar
  • 2j Oishi T. Katayama T. Yamaguchi K. Mizuno N. Chem. Eur. J.  2009,  15:  7539 
    Search in Google Scholar
  • For representative papers on the synthesis of disulfides by dehydrogenative homocoupling reactions, see:
  • 3a Arterburn JB. Perry MC. Nelson SL. Dible BR. Holguin MS. J. Am. Chem. Soc.  1997,  119:  9309 
    Search in Google Scholar
  • 3b Singh D. Galetto FZ. Soares LC. Rodrigues OED. Braga AL. Eur. J. Org. Chem.  2010,  14:  2661 
    Search in Google Scholar
  • 3c Banfield SC. Omori AT. Leisch H. Hudlicky T.
    J. Org. Chem.  2007,  72:  4989 
    Search in Google Scholar
  • 3d Choi J. Yoon NM.
    J. Org. Chem.  1995,  60:  3266 
    Search in Google Scholar
  • 3e Ramesha AR. Chamedarsekran S. J. Org. Chem.  1994,  59:  1354 
    Search in Google Scholar
  • 4a Rosenberg L. Davis CW. Yao J.-Z. J. Am. Chem. Soc.  2001,  123:  5120 
    Search in Google Scholar
  • 4b Braunstein P. Morise X. Chem. Rev.  2000,  100:  3541 
    Search in Google Scholar
  • 5a Kajimoto T. Takahashi H. Tsuji J. Bull. Chem. Soc. Jpn.  1982,  55:  3673 
    Search in Google Scholar
  • 5b For an excellent report on copper-catalyzed dehydrogenative coupling of anilines leading to azo compounds, see: Zhang C. Jiao N. Angew. Chem. Int. Ed.  2010,  49:  6174 
    Search in Google Scholar
  • 6a Hydrazine and Its Derivatives, In Kirk-Othmer Encyclopedia of Chemical Technology   Vol. 13, 4th ed.:  Wiley; New York: 1995. 
  • 6b Encyclopedia of Reagents for Organic Synthesis   Paquette LA. Wiley; Chichester: 1995. 
  • 6c Ragnarsson U. Chem. Soc. Rev.  2001,  30:  205 
    Search in Google Scholar
  • 7a Han H. Janda KD. J. Am. Chem. Soc.  1996,  118:  2539 
    Search in Google Scholar
  • 7b Zhang R. Durkin JP. Windsor WT. Bioorg. Med. Chem. Lett.  2002,  12:  1005 
    Search in Google Scholar
  • 7c Lee T.-W. Cherney MM. Huitema C. Liu J. James KE. Powers JC. Eltis LD. James MNG. J. Mol. Biol.  2005,  353:  1137 
    Search in Google Scholar
  • For representative papers for the synthesis of hydrazines from the compounds containing N-N or N=N bonds, see:
  • 8a Bredihhin A. Groth UM. Maeorg U. Org. Lett.  2007,  9:  1097 
    Search in Google Scholar
  • 8b Kisseljova K. Tsubrik O. Org. Lett.  2006,  8:  43 
    Search in Google Scholar
  • 8c Bredihhin A. Maeorg U. Org. Lett.  2007,  9:  4975 
    Search in Google Scholar
  • 8d Maeorg U. Grehn L. Ragnarsson U. Angew. Chem. Int. Ed.  1996,  35:  2626 
    Search in Google Scholar
  • 8e Rosamilia AE. Aricò F. Tundo P. J. Org. Chem.  2008,  73:  1559 
    Search in Google Scholar
  • 8f Tsubrik O. Maeorg U. Org. Lett.  2001,  3:  2297 
    Search in Google Scholar
  • 8g Alberti A. Canè F. Dembech P. Lazzari D. Ricci A. Seconi G. J. Org. Chem.  1996,  61:  1677 
    Search in Google Scholar
  • 8h Brosse N. Pinto M.-F. Bodiguel J. Jamart-Gregoire B. J. Org. Chem.  2001,  66:  2869 
    Search in Google Scholar
  • 8i Grehn L. Lohn H. Ragnarsson U. Chem. Commun.  1997,  15:  1381 
    Search in Google Scholar
  • 8j Brosse N. Pinto M.-F. Jamart-Gregoire B. J. Org. Chem.  2000,  65:  4370 
    Search in Google Scholar
  • 8k Maeorg U. Ragnarsson U. Tetrahedron Lett.  1998,  39:  681 
    Search in Google Scholar
  • 8l Maeorg U. Pehk T. Ragnarsson U. Acta Chem. Scand.  1999,  53:  1127 
    Search in Google Scholar
  • 8m Bredihhin A. Maeorg U. Tetrahedron  2008,  64:  6788 
    Search in Google Scholar
  • 8n Tsubrik O. Maeorg U. Sillard R. Ragnarsson U. Tetrahedron  2004,  60:  8363 
    Search in Google Scholar
  • 9 Vidal J. Hannachi J.-C. Hourdin G. Mulatier J.-C. Collet A. Tetrahedron Lett.  1998,  39:  8845 
    CrossrefSearch in Google Scholar
  • 10 Huddleston PR. Coutts GC. Comprehensive Organic Functional Group Transformations   Vol. 2:  Katritzky AR. Meth-Cohn O. Rees CW. Pergamon/Elsevier; Oxford: 1995.  p.371-383  
    Search in Google Scholar
  • 11 Furst A. Moore RE. J. Am. Chem. Soc.  1957,  79:  5492 
    CrossrefSearch in Google Scholar
  • 12 Similarly, inorganic metal oxide MnO2 promoted an oxygen-mediated oxidation: Joyce LL. Batey RA. Org. Lett.  2009,  11:  2792 
    CrossrefPubMedSearch in Google Scholar
  • 13a Steinhoff BA. King AE. Stahl SS. J. Org. Chem.  2006,  71:  1861 
    Search in Google Scholar
  • 13b Schultz MJ. Hamilton SS. Jensen DR. Sigman MS. J. Org. Chem.  2005,  70:  3343 
    Search in Google Scholar
  • 15a Lewis EA. Tolman WB. Chem. Rev.  2004,  104:  1047 
    Search in Google Scholar
  • 15b Mirica LM. Ottenwaelder X. Stack TDP. Chem. Rev.  2004,  104:  1013 
    Search in Google Scholar
  • 15c Collman JP. Zhong M. Zhang C. Costanzo S. J. Org. Chem.  2001,  66:  7892 
    Search in Google Scholar
14

General Experimental Procedure: To a solution of N-alkylaniline 1 (0.107 g, 1.0 mmol) in DMF (2 mL) were added CuBr (0.029 g, 0.2 mmol), TMEDA (0.232 g, 2.0 mmol), CuO (0.016 g, 0.2 mmol), K2CO3 (0.276 g, 2.0 equiv) and 4 Å MS (0.1 g) successively, and the reaction mixture was stirred at 70 ˚C or 95 ˚C for 12-24 h in air. After the reaction was completed, the mixture was filtered, and the residue was washed with EtOAc (3 × 5 mL). Then, the combined filtrates were concentrated in vacuum, and the residue was purified by column chromatography (silica gel, PE-EtOAc as eluent) to afford the desired hydrazine 2.