Synthesis 2007(16): 2517-2523  
DOI: 10.1055/s-2007-983810
PAPER
© Georg Thieme Verlag Stuttgart · New York

Short and Practical Synthesis of N′,N′-Disubstituted N-Aryl-1,2-Ethylene­diamines by a Decarboxylative Ring-Opening Reaction under Nucleophilic Conditions

Yasuhiro Morita, Takeshi Ishigaki, Kuniaki Kawamura, Katsuhiko Iseki*
Toray Industries Inc., Pharmaceutical Research Laboratories, 6-10-1 Tebiro, Kamakura, Kanagawa 248-8555, Japan
Fax: +81(467)322127; e-Mail: Katsuhiko_Iseki@nts.toray.co.jp;
Further Information

Publication History

Received 30 March 2007
Publication Date:
24 July 2007 (online)

Abstract

A straightforward and practical synthesis of N′,N′-disubstituted N-aryl-1,2-ethylenediamines, starting from anilines, via N-aryloxazolidin-2-ones is described. A decarboxylative ring-opening reaction of N-aryloxazolidin-2-ones, using aliphatic secondary amines, is the key step in this procedure. A one-pot synthesis of N-aryloxazolidin-2-ones is also described. N′,N′-Disubstituted N-aryl-1,2-ethylenediamines are a useful building block for biologically active compounds.

    References

  • 1a Roth GJ, Heckel A, Walter R, Meel JV, Redemann N, Tontsch-Grunt U, Spevak W, and Hilberg F. inventors; US  6762180. 
  • 1b Sato S, Yukawa H, Kihara Y, Koga N, Saito M, and Nishi T. inventors; WO  9304042. 
  • 2a Hopff H, Spaenig H, and Schuster C. inventors; US  2623880. 
  • 2b Cross PE, and Leeming PR. inventors; UK  1306450. 
  • 2c Parimoo P. Grabowski BF. Haney WG. J. Pharm. Sci.  1972,  61:  974 
  • 3a Pratesi P. Villa L. Ferri V. Grana E. Sossi D. Farmaco, Ed. Sci.  1969,  24:  313 
  • 3b Cappello B. Silipo C. Vittoria A. Farmaco, Ed. Sci.  1984,  39:  991 
  • 4 For a recent review, see: Meléndez RE. Lubell WD. Tetrahedron  2003,  59:  2581 ; and references cited therein
  • 5a Poindexter GS. J. Heterocycl. Chem.  1983,  20:  1431 
  • 5b Poindexter GS. inventors; US  4381401. 
  • 5c Rooney PC, and Nutt MO. inventors; US  5491263. 
  • 6 Poindexter GS. Owens DA. Dolan PL. Woo E. J. Org. Chem.  1992,  57:  6257 ; and references cited therein
  • 7a For a review, see: Dyen ME. Swern D. Chem. Rev.  1967,  67:  197 
  • For selected examples, see:
  • 7b Najer H. Chabrier P. Giudicelli R. Menin J. Duchemin J. Bull. Soc. Chim. Fr.  1959,  1841 
  • 7c Gabriel S. Eschenbach G. Ber. Dtsch. Chem. Ges.  1897,  30:  2494 
  • 8 Mallesham B. Rajesh BM. Rajamohan R. Srinivas D. Trehan S. Org. Lett.  2003,  5:  963 ; and references cited therein
  • 9 Lang G, and Junino A. inventors; US  4910341. For a review, see:
  • 10 Harada M, Matsushita A, and Yoshii K. inventors; Jpn. Kokai Tokkyo Koho  147578. 
  • 11 For a review, see: Pankratov VA. Frenkel TsM. Fainleib AM. Russian Chem. Rev.  1983,  52:  576 ; Recently Pd and Cu-catalyzed coupling of oxazolidine-2-ones with aryl halides was reported, see: ref 8 and 12
  • 12 Yin J. Buchwald SL. J. Am. Chem. Soc.  2002,  124:  6043 
  • 13 Wright WmB. Brabander HJ. Hardy RA. J. Org. Chem.  1961,  26:  476 
  • 14a Hoeglund IPJ. Silver S. Engstroem MT. Salo H. Tauber A. Kyyroenen H.-K. Saarenketo P. Hoffren A.-M. Kokko K. Pohjanoksa K. Sallinen J. Savola J.-M. Wurster S. Kallatsa OA. J. Med. Chem.  2006,  49:  6351 
  • 14b Sablle S. inventors; EP  1568683 A2. 
  • 15 Stubbins JF. Soine TO. J. Pharm. Sci.  1966,  55:  1093 
  • 16 Mckay AF. Braun RO. J. Org. Chem.  1951,  16:  1829 
  • 17 Chiang GCH. Olsson T. Org. Lett.  2004,  6:  3079