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Synthesis 2010(9): 1433-1440  
DOI: 10.1055/s-0029-1218675
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Efficient Synthesis of β-Oxoalkyl Carbamates from Carbon Dioxide, Internal Propargylic Alcohols, and Secondary Amines Catalyzed by Silver Salts and DBU

Chaorong Qi, Liangbin Huang, Huanfeng Jiang*
School of Chemistry and Chemical Engineering, South China University of Technology, 381 Wushan Road, Guangzhou 510640, P. R. of China
Fax: +86(20)87112906; e-Mail: jianghf@scut.edu.cn;
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Publication History

Received 14 December 2009
Publication Date:
11 February 2010 (online)

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Abstract

The three-component reaction of internal propargylic alcohols with secondary amines and carbon dioxide proceeded smoothly in the presence of a catalyst system comprising a silver salt and 1,8-diazabicyclo[5.4.0]undec-7-ene in 1,4-dioxane at 90 ˚C to give the corresponding β-oxoalkyl carbamates in good to high yields. The counterion of the silver salt had little effect on the reaction whereas the nature of the organic base had a marked influence.

Key words

amines - carbamates - carbon dioxide - catalysis - propargylic alcohols

    References

  • 1a Sakakura H. Choi J.-C. Yasuda H. Chem. Rev.  2007,  107:  2365 
    Google Scholar
  • 1b Darensbourg DJ. Chem. Rev.  2007,  107:  2388 
    Google Scholar
  • 1c Beckman EJ. Ind. Eng. Chem. Res.  2003,  42:  1598 
    Google Scholar
  • 1d Shi M. Shen Y.-M. Curr. Org. Chem.  2003,  7:  737 
    Google Scholar
  • 2a Salvatore RN. Flanders VL. Ha D. Jung KW. Org. Lett.  2000,  2:  2797 
    Google Scholar
  • 2b Yoshida D. Hara N. Okuyama S. Chem. Commun.  2000,  151 
    Google Scholar
  • 2c Rohr M. Geyer C. Wandeler R. Schneider MS. Murphy EF. Baiker A. Green Chem.  2001,  3:  123 
    Google Scholar
  • 2d Salvatore SI. Shin SI. Nagle AS. Jung KWJ. Org. Chem.  2001,  66:  1035 
    Google Scholar
  • 2e Abla M. Choi J.-C. Sakakura T. Chem. Commun.  2001,  2238 
    Google Scholar
  • 2f Feroci M. Casadei MA. Orsini M. Palombi L. Inesi A. J. Org. Chem.  2003,  68:  1548 
    Google Scholar
  • 2g Srivastava R. Srinivas D. Ratnasamy P. Appl. Catal. A  2005,  289:  128 
    Google Scholar
  • 2h Chaturvedi D. Ray S. Monatsh. Chem.  2006,  137:  127 
    Google Scholar
  • 2i Chaturvedi D. Mishra N. Mishra V. Monatsh. Chem.  2007,  138:  57 
    Google Scholar
  • 3a Vauthey I. Valot F. Gozzi C. Fache F. Lemaire M. Tetrahedron Lett.  2000,  41:  6347 
    Google Scholar
  • 3b Wu TT. Huang J. Arrington ND. Dill GM. J. Agric. Food Chem.  1987,  35:  817 
    Google Scholar
  • 3c Barthelemy L. Lyon Pharm.  1986,  37:  249 
    Google Scholar
  • 3d Adams P. Baron FA. Chem. Rev.  1965,  65:  567 
    Google Scholar
  • 4 Green TW. Wuts PGM. Protective Groups in Organic Synthesis   2nd ed.:  Wiley; New York: 1999.  p.315-318  
    Google Scholar
  • 5a Sasaki Y. Dixneuf PH. J. Org. Chem.  1987,  52:  4389 
    Google Scholar
  • 5b Burncau C. Dixneuf PH. Tetrahedron Lett.  1987,  28:  2005 
    Google Scholar
  • 5c Sasaki Y. inventors; JP  62061961(A).  ; Chem. Abstr. 1988, 108, 204234
  • 6 Kim TJ. Kwon KH. Kwon SC. Baeg JO. Shim SC. Lee DH. J. Organomet. Chem.  1990,  389:  205 
    CrossrefGoogle Scholar
  • 7 Shim SC. Baeg JO. Doh CH. Young YZ. Kim TJ. Bull. Korean Chem. Soc.  1990,  11:  467 
    Google Scholar
  • 8a Kim H.-S. Kim J.-W. Kwon S.-C. Shim S.-C. Kim T.-J. J. Organomet. Chem.  1997,  545-546:  337 
    Google Scholar
  • 8b Kwon S.-C. Cho S.-C. Shim S.-C. Kim T.-J. Bull. Korean Chem. Soc.  1999,  20:  103 
    Google Scholar
  • 9a Qi CR. Jiang HF. Wang ZY. Zou B. Yang SR. Synlett  2007,  255 
    Google Scholar
  • 9b Qi CR. Jiang HF. Wang ZY. Zou B. Chin. J. Chem.  2007,  25:  1051 
    Google Scholar
  • 9c Qi CR. Jiang HF. Liu HL. Yang SR. Zou B. Gaodeng Xuexiao Huaxue Xuebao  2007,  28:  1084 ; Chem. Abstr. 2007, 148, 538111
    Google Scholar
  • 9d Jiang HF. Wang AZ. Liu HL. Qi CR. Eur. J. Org. Chem.  2008,  2309 
    Google Scholar
  • 9e Jiang H. Zhao J. Wang A. Synthesis  2008,  763 
    Google Scholar
  • 9f Jiang HF. Zhao JW. Tetrahedron Lett.  2009,  50:  60 
    Google Scholar
  • 10 Qi CR. Jiang HF. Green Chem.  2007,  9:  1284 
    CrossrefGoogle Scholar
  • 13a Bruneau C. Dixneuf PH. J. Mol. Catal.  1992,  74:  97 
    Google Scholar
  • 13b Inoue Y. Ishikawa J. Taniguchi M. Hashimoto H. Bull. Chem. Soc. Jpn.  1987,  60:  1204 
    Google Scholar
  • 13c Fujiwara S. Shikano Y. Shinike T. Kambe N. Sonoda N. J. Org. Chem.  2002,  67:  6275 
    Google Scholar
  • 13d Kayaki Y. Yamamoto M. Suzuki T. Ikariya T. Green Chem.  2006,  8:  1019 
    Google Scholar
  • 13e Yamada W. Sugawara Y. Cheng HM. Ikeno T. Yamada T. Eur. J. Org. Chem.  2007,  2604 
    Google Scholar
11

(4Z)-4-Benzylidene-1,3-dioxaspiro[4.5]decan-2-one could be quantitatively transformed into 3a by treatment with Et2NH (1 equiv) in 1,4-dioxane at 90 ˚C for 15 h.

12

When a primary amine(butylamine) was used under the same conditions, 4-benzylidene-3-butyl-1-oxa-3-azaspiro[4.4]nonan-2-one was obtained in 81% yield (E/Z = 52:48).