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Synlett 2010(5): 809-811  
DOI: 10.1055/s-0029-1219384
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

(PPh3)AuCl/AgOTf-Catalyzed Intermolecular Hydroamination of Alkynes with Sulfonamides To Form N-Sulfonyl Imines

Dong-Mei Cui*a, Jin-Zhou Zhenga, Liu-Yang Yanga, Chen Zhangb
a College of Pharmaceutical Science, Zhejiang University of Technology, Hangzhou 310014, P. R. of China
Fax: +86(571)88320320; e-Mail: cuidongmei@zjut.edu.cn;
b School of Pharmaceutical Sciences, Zhejiang University, Hangzhou 310058, P. R. of China
Further Information

Publication History

Received 9 October 2009
Publication Date:
10 February 2010 (online)

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Abstract

In the presence of a catalytic amount of (PPh3)AuCl and AgOTf, intermolecular hydroamination of unactivated alkynes with sulfonamides has been shown to proceed and give N-sulfonyl ketimines in medium to excellent yields.

Key words

hydroamination - N-sulfonyl ketimines - sulfonamide - alkyne - gold catalysis

    References and Notes

  • 1a Weinreb SM. Top. Curr. Chem.  1997,  190:  131 
    Google Scholar
  • 1b Bloch R. Chem. Rev.  1998,  98:  1407 
    Google Scholar
  • 2a Ram RN. Khan AA. Synth. Commun.  2001,  31:  841 
    Google Scholar
  • 2b Jin T. Feng G. Yang M. Li T. Synth. Commun.  2004,  34:  1277 
    Google Scholar
  • 2c Love BE. Raje PS. Willimas TCII. Synlett  1994,  493 
    Google Scholar
  • 3a Artman GD. Bartolozzi A. Franck RW. Weinreb SM. Synlett  2001,  232 
    Google Scholar
  • 3b Brown C. Hudson RF. Record KAF. J. Chem. Soc., Perkin Trans. 2  1978,  822 
    Google Scholar
  • 4 Boger DL. Corbett WL. J. Org. Chem.  1992,  57:  4777 
    CrossrefGoogle Scholar
  • 5 Wolfe JP. Ney JE. Org. Lett.  2003,  5:  4607 
    CrossrefPubMedGoogle Scholar
  • 6 Ruano JLG. Alemán J. Cid MB. Parra A. Org. Lett.  2005,  7:  179 
    CrossrefPubMedGoogle Scholar
  • Recent reviews, see:
  • 7a Gorin DJ. Sherry BD. Toste FD. Chem. Rev.  2008,  108:  3351 
    Google Scholar
  • 7b Jiménez-Núñez E. Echavarren AM. Chem. Rev.  2008,  108:  3326 
    Google Scholar
  • 7c Arcadi A. Chem. Rev.  2008,  108:  3266 
    Google Scholar
  • 7d Li Z. Brouwer C. He C. Chem. Rev.  2008,  108:  3239 
    Google Scholar
  • 7e Skouta R. Li C.-J. Tetrahedron  2008,  64:  4917 
    Google Scholar
  • 7f Shen HC. Tetrahedron  2008,  64:  3885 
    Google Scholar
  • 7g Muzart J. Tetrahedron  2008,  64:  5815 
    Google Scholar
  • 7h Hashmi ASK. Chem. Rev.  2007,  107:  3180 
    Google Scholar
  • 7i Hashmi ASK. Gold Bull.  2004,  37:  51 
    Google Scholar
  • 7j Arcadi A. Di Giuseppe S. Curr. Org. Chem.  2004,  8:  795 
    Google Scholar
  • 7k HashmiA SK. Hutchings GJ. Angew. Chem. Int. Ed.  2006,  45:  7896 
    Google Scholar
  • Selected references:
  • 8a Shapiro ND. Toste FD. J. Am. Chem. Soc.  2007,  129:  4160 
    Google Scholar
  • 8b Dube P. Toste FD. J. Am. Chem. Soc.  2006,  128:  12062 
    Google Scholar
  • 8c Marion N. Díez-González S. de Frémont P. Noble AR. Nolan SP. Angew. Chem. Int. Ed.  2006,  45:  3647 
    Google Scholar
  • 8d Zhang Y. Donahue JP. Li C.-J. Org. Lett.  2007,  9:  627 
    Google Scholar
  • 8e Mizushima E. Sato K. Hayashi T. Tanaka M. Angew. Chem. Int. Ed.  2002,  41:  4563 
    Google Scholar
  • 8f Liu B. De Brabander JK. Org. Lett.  2006,  8:  4907 
    Google Scholar
  • 8g Mizushima E. Hayashi T. Tanaka M. Org. Lett.  2003,  5:  3349 
    Google Scholar
  • 8h Arcadi A. Di Giuseppe S. Marinelli F. Rossi E. Adv. Synth. Catal.  2001,  343:  443 
    Google Scholar
  • 8i Hashmi ASK. Weyrauch JP. Frey W. Bats JW. Org. Lett.  2004,  6:  4391 
    Google Scholar
  • 8j Luo YM. Li ZG. Li CJ. Org. Lett.  2005,  7:  2675 
    Google Scholar
  • 8k Lavallo V. Frey GD. Donnadieu B. Soleihavoup M. Bertrand G. Angew. Chem. Int. Ed.  2008,  47:  5224 
    Google Scholar
  • 9 Yin Y. Ma W. Chai Z. Zhao G. J. Org. Chem.  2007,  72:  5731 
    Google Scholar
  • 10a Hiroya K. Matsumoto S. Sakamoto T. Org. Lett.  2004,  6:  2953 
    Google Scholar
  • 10b Hiroya K. Matsumoto S. Ashikawa M. Kida H. Sakamoto T. Tetrahedron  2005,  61:  12330 
    Google Scholar
  • 10c Wolf LB. Tjen KCMF. ten Brink HT. Blaauw RH. Hiemstra H. Schoemaker HE. Rutjes FPJT. Adv. Synth. Catal.  2002,  344:  70 
    Google Scholar
  • 11a Hiroya K. Itoh S. Sakamoto T. Tetrahedron  2005,  61:  10958 
    Google Scholar
  • 11b Hiroya K. Itoh S. Ozawa M. Kanamori Y. Sakamoto T. Tetrahedron Lett.  2002,  43:  1277 
    Google Scholar
  • 12 Barange DK. Nishad TC. Swamy NK. Bandameedi V. Kumar D. Sreekanth BR. Vyas K. Pal M. J. Org. Chem.  2007,  72:  8547 
    CrossrefPubMedGoogle Scholar
  • 13 Istrate FM. G agosz F. Org. Lett.  2007,  9:  3181 
    CrossrefPubMedGoogle Scholar
  • 14 Kurisaki T. Naniwa T. Yamamoto H. Imagawa H. Nishizawa M. Tetrahedron Lett.  2007,  48:  1871 
    CrossrefGoogle Scholar
  • 15 For intermolecular addition of sulfonamides to conjugated alkynoates, see: Trost BM. Dake GR. J. Am. Chem. Soc.  1997,  119:  7595 
    CrossrefGoogle Scholar
  • 16a Liu X.-Y. Ding P. Huang J.-S. Che CM. Org. Lett.  2007,  9:  2645 
    Google Scholar
  • 16b Fukuda Y. Utimoto K. Nozaki H. Heterocycles  1987,  25:  297 
    Google Scholar
  • 16c Müller TE. Tetrahedron Lett.  1998,  39:  5961 
    Google Scholar
  • 16d Hashmi ASK. Rudolph M. Schymura S. Visus J. Frey W. Eur. J. Org. Chem.  2006,  4905 
    Google Scholar
  • 17a Zhang C. Cui D.-M. Yao L.-Y. Wang B.-S. Hu Y.-Z. Hayashi T. J. Org. Chem.  2008,  73:  7811 
    Google Scholar
  • 17b Cui D.-M. Zheng Z.-L. Zhang C. J. Org. Chem.  2009,  74:  1426 
    Google Scholar
  • 17c Cui D.-M. Meng Q. Zheng J.-Z. Zhang C. Chem. Commun.  2009,  1577 
    Google Scholar
  • 17d Cui D.-M. Yu K.-R. Zhang C. Synlett  2009,  1103 
    Google Scholar
  • 18 Zhang J. Yang C.-G. He C. J. Am. Chem. Soc.  2006,  128:  1798 
    Google Scholar
19

Typical Experimental Procedure
To a reactor containing sulfonamide (0.5 mmol), (PPh3)AuCl (0.01 mmol), AgOTf (0.04 mmol), and anhyd toluene (2 mL), was added alkyne (1.5 mmol). The mixture was then sealed and stirred at 100 °C. After 9 h, it was quenched with sat. soln of NaHCO3 and then with EtOAc
(3 ¥ 10 mL), dried over Na2SO4, and concentrated in vacuo. The residue was purified by flash chromatography to give the pure product. N -[1-(4-Ethoxyphenyl)ethylidene]-4-methylbenzene-sulfonamide (3b)
Yellow solid; mp 103-105 °C. ¹H NMR (500 MHz, CDCl3): d = 7.92-7.88 (m, 4 H), 7.32 (d, J = 8.0 Hz, 2 H), 6.86 (d, J = 9.0 Hz, 2 H), 4.06 (q, J = 7.0 Hz, 2 H), 2.92 (s, 3 H), 2.43 (s, 3 H), 1.41 (t, J = 7.0 Hz, 3 H). ¹³C NMR (125 MHz, CDCl3): d = 178.7, 163.4, 143.3, 139.1, 130.7, 129.7, 129.4, 127.0, 114.3, 63.9, 21.6, 20.7, 14.6. IR (KBr): 2980, 2936, 2884, 1607, 1578, 1557, 1385, 1173, 1150 cm-¹. HRMS (CI): m/z calcd for C17H19NO3S [M + H]+: 318.1164; found: 318.1164.
N -[1-(4-Methoxyphenyl)ethylidene]methane-sulfonamide (3l)
Pale yellow solid; mp 107-108 °C. ¹H NMR (500 MHz, CDCl3): d = 7.94 (d, J = 9.0 Hz, 2 H), 6.93 (d, J = 9.0 Hz, 2 H), 3.88 (s, 3 H), 3.22 (s, 3 H), 2.86 (s, 3 H). ¹³C NMR (125 MHz, CDCl3): d = 178.9, 163.9, 130.5, 129.6, 114.0, 55.6, 43.2, 20.8. IR (KBr): 3032, 2937, 1635, 1609, 1595, 1384, 1182, 1143 cm-¹. HRMS (EI): m/z calcd for C10H13NO3S [M]+: 227.0616; found: 227.0612.