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Synthesis 2012(5): 705-710  
DOI: 10.1055/s-0031-1289693
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Efficient and Divergent Synthesis of Functionalized Cyclopropanes via Iodoform Reaction

Dingyuan Zhang, Rui Zhang, Dexuan Xiang, Ning Zhang*, Yongjiu Liang, Dewen Dong*
Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, P. R. of China
Fax: +86(431)85262676; e-Mail: zhangningtum@gmail.com; e-Mail: dwdong@ciac.jl.cn;
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Publication History

Received 26 November 2011
Publication Date:
03 February 2012 (online)

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Abstract

Efficient and divergent one-pot synthesis of cyclopropyl amides and esters from readily available 1-acetylcyclopropanes via iodoform reaction based on the selection of reaction conditions is reported. A series of substituted cyclopropyl amides were synthesized from 1-acetylcyclopropanes, iodine, and ammonia in water in the presence of K2CO3 in good yields, whereas substituted cyclopropyl esters were obtained from the reaction of 1-acetylcyclopropanes with iodine and alcohols in the presence of DBU.

Key words

cyclopropanes - iodoform reaction - iodine - amide - water­

    References

  • For reviews on cyclopropanes, see:
  • 1a Wong HNC. Hon MY. Tse CW. Yip YC. Tanko J. Hudlicky T. Chem. Rev.  1989,  89:  165 
    Search in Google Scholar
  • 1b Kulinkovich OG. Chem. Rev.  2003,  103:  2597 
    Search in Google Scholar
  • 1c Brackmann F. de Meijere A. Chem. Rev.  2007,  107:  4493 
    Search in Google Scholar
  • 1d Gnad F. Reiser O. Chem. Rev.  2003,  103:  1603 
    Search in Google Scholar
  • 1e Noyori R. Angew. Chem. Int. Ed.  2002,  41:  2008 
    Search in Google Scholar
  • 2a Vinogradov MG. Kaigorodova LN. Chel’tsova-Bebutova GV. Gorshkova LS. Starostin EK. Nikishin GL. Ignatenko AV. Shapiro EA. Russ. Chem. Bull.  1995,  44:  167 
    Search in Google Scholar
  • 2b Kaneko H. J. Agric. Food Chem.  2011,  59:  2786 
    Search in Google Scholar
  • 2c Graham DW. Ashton WT. Barash L. Brown JE. Brown RD. Canning LF. Chen A. Springer JP. Rogers EF. J. Med. Chem.  1987,  30:  1074 
    Search in Google Scholar
  • 2d Krief A. Froidbisea A. Tetrahedron  2004,  60:  7637 
    Search in Google Scholar
  • For reviews, see:
  • 3a Hoveyda AH. Evans DA. Fu GC. Chem. Rev.  1993,  93:  1307 
    Search in Google Scholar
  • 3b Charette AB. Marcoux J.-F. Synlett  1995,  1197 
  • 3c Lautens M. Klute W. Tam W. Chem. Rev.  1996,  96:  49 
    Search in Google Scholar
  • 3d Charette AB. Lebel H. In Comprehensive Asymmetric Catalysis   Jacobsen EN. Pfaltz A. Yamamoto H. Springer-Verlag; Berlin: 1999.  Chap. 16.3.
  • 3e Lebel H. Marcoux J.-F. Molinaro C. Charette AB. Chem. Rev.  2003,  103:  977 
    Search in Google Scholar
  • For references, see:
  • 4a Simmons HE. Smith RD. J. Am. Chem. Soc.  1958,  80:  5323 
    Search in Google Scholar
  • 4b Simmons HE. Smith RD. J. Am. Chem. Soc.  1959,  81:  4256 
    Search in Google Scholar
  • 4c Rawson RJ. Harrison IT. J. Org. Chem.  1970,  35:  2057 
    Search in Google Scholar
  • 4d Nishimura J. Furukawa J. Kawabata N. Kitayama M. Tetrahedron  1971,  27:  1799 
    Search in Google Scholar
  • 4e Friedrich EC. Lunetta SE. Lewis EJ. J. Org. Chem.  1989,  54:  2388 
    Search in Google Scholar
  • 4f Charette AB. Marcoux J.-F. Molinaro C. Beauchemin A. Brochu C. Isabel E. J. Am. Chem. Soc.  2000,  122:  4508 
    Search in Google Scholar
  • 5a Shimamoto K. Ishida M. Shinozaki H. Ohfune Y.
    J. Org. Chem.  1991,  56:  4167 
    Search in Google Scholar
  • 5b Shimamoto K. Ohfune Y. Tetrahedron Lett.  1989,  30:  3802 
    Search in Google Scholar
  • 5c Hanessian S. Murray PJ. J. Org. Chem.  1987,  52:  1170 
    Search in Google Scholar
  • 5d Vangveravong S. Nichols DE. J. Org. Chem.  1995,  60:  3409 
    Search in Google Scholar
  • 5e Pietruszka J. Widenmeyer M. Synlett  1997,  977 
  • 5f Luithle JEA. Pietruszka J. J. Org. Chem.  1999,  64:  8287 
    Search in Google Scholar
  • 5g Pietruszka J. Witt A. J. Chem. Soc., Perkin Trans. 1  2000,  4293 
  • 5h Luithle JEA. Pietruszka J. J. Org. Chem.  2000,  65:  9194 
    Search in Google Scholar
  • 6a de Meijere A. Bagutski V. Zeuner F. Fischer UK. Rheinberger V. Moszner N. Eur. J. Org. Chem.  2004,  3669 
  • 6b Yang Y. Shi M. J. Org. Chem.  2005,  70:  8645 
    Search in Google Scholar
  • 6c Su J. Xiong J. Liang S. Qiu G. Feng X. Teng H. Wu L. Hu X. Synth. Commun.  2006,  36:  693 
    Search in Google Scholar
  • 6d Ronsisvalle G. Marrazzo A. Prezzavento O. Pasquinucci L. Falcucci B. Toro RD. Spampinato S. Bioorg. Med. Chem.  2000,  8:  1503 
    Search in Google Scholar
  • 7a Pan W. Dong D. Wang K. Zhang J. Wu R. Xiang D. Liu Q. Org. Lett.  2007,  9:  2421 
    Search in Google Scholar
  • 7b Fu X. Huang P. Zhou G. Hu Y. Dong D. Tetrahedron  2011,  67:  6347 
    Search in Google Scholar
  • 7c Wang K. Fu X. Liu J. Liang Y. Dong D. Org. Lett.  2009,  11:  1015 
    Search in Google Scholar
  • 7d Wang K. Xiang D. Liu J. Pan W. Dong D. Org. Lett.  2008,  10:  1691 
    Search in Google Scholar
  • For Iodoform reactions, see:
  • 8a Fuson RC. Bull BA. Chem. Rev.  1934,  15:  275 
    Search in Google Scholar
  • 8b Fuson RC. Tullock CW. J. Am. Chem. Soc.  1934,  56:  1638 
    Search in Google Scholar
  • 8c Arnold RT. Buckles R. Stoltenberg J. J. Am. Chem. Soc.  1944,  66:  208 
    Search in Google Scholar
  • For the conversion of acetyl into amide and ester group, see:
  • 8d Cao L. Ding J. Gao M. Wang Z. Li J. Wu A. Org. Lett.  2009,  11:  3810 
    Search in Google Scholar
  • 8e Yin G. Gao M. Wang Z. Wu Y. Wu A. Bull. Chem. Soc. Jpn.  2008,  81:  369 
    Search in Google Scholar
  • 9 For the preparation of 1-acetyl-1-carbamoylcyclopropanes, see: Zhang Z. Zhang Q. Sun S. Xiong T. Liu Q. Angew. Chem. Int. Ed.  2007,  46:  1726 
    Search in Google Scholar
  • 10a Aqueous-Phase Organometallic Catalysis: Concepts and Applications   Cornils B. Herrmann WA. Wiley-VCH; Weinheim: 1998. 
  • 10b Organic Synthesis in Water   Grieco PA. Blackie Academic and Professional; London: 1998. 
  • 10c Organic Reactions in Aqueous Media   Li C.-J. Chan T.-H. Wiley; New York: 1997. 
  • 10d Kobayashi S. Manabe K. In Stimulating Concepts in Chemistry   Shibasaki M. Stoddart JF. Vögtle F. Wiley-VCH; Weinheim: 2000. 
  • 11a Li CJ. Chem. Rev.  1993,  93:  2023 
    Search in Google Scholar
  • 11b Fringuelli F. Piermatti O. Pizzo F. Vaccaro L. Eur. J. Org. Chem.  2001,  439 
  • 11c Kobayashi S. Manabe K. Acc. Chem. Res.  2002,  35:  209 
    Search in Google Scholar
  • 12a Manabe K. Mori Y. Kobayashi S. Synlett  1999,  1401 
  • 12b Manabe K. Kobayashi S. Org. Lett.  1999,  1:  1965 
    Search in Google Scholar
  • 12c Otto S. Engberts JBSN. Kwak JCT. J. Am. Chem. Soc.  1998,  120:  9517 
    Search in Google Scholar
  • 12d Rispens T. Engberts JBSN. Org. Lett.  2001,  3:  941 
    Search in Google Scholar
  • 12e Manabe K. Sun XM. Kobayashi S. J. Am. Chem. Soc.  2001,  123:  10101 
    Search in Google Scholar
  • 12f Ouyang Y. Dong D. Yu H. Liang Y. Liu Q. Adv. Synth. Catal.  2006,  348:  206 
    Search in Google Scholar
  • For selected work on the conversion of amide into cyano group, see:
  • 14a Mowry DT. Chem. Rev.  1948,  42:  189 
    Search in Google Scholar
  • 14b Rickborn B. Jensen FR. J. Org. Chem.  1962,  27:  4608 
    Search in Google Scholar
  • 14c Lehnert W. Tetrahedron Lett.  1971,  19:  1501 
    Search in Google Scholar
  • 14d Ellzey SE. Mack CH. Connick WJ. J. Org. Chem.  1967,  32:  846 
    Search in Google Scholar
  • For selected examples on ring-opening or ring-enlargement reactions of cyclopropanes, see:
  • 15a Bernard AM. Frongia A. Piras PP. Secci F. Spiga M. Org. Lett.  2005,  7:  4565 
    Search in Google Scholar
  • 15b Ogoshi S. Nagata M. Kurosawa H. J. Am. Chem. Soc.  2006,  128:  5350 
    Search in Google Scholar
  • 15c Liu L. Montgomery J.
    J. Am. Chem. Soc.  2006,  128:  5348 
    Search in Google Scholar
  • 15d Ma S. Zhang J. Angew. Chem. Int. Ed.  2003,  42:  183 
    Search in Google Scholar
  • For selected references on Vilsmeier reagents, see:
  • 16a Marson CM. Tetrahedron  1992,  48:  3659 
    Search in Google Scholar
  • 16b Meth-Cohn O. Tarnowski B. Adv. Heterocycl. Chem.  1982,  31:  207 
    Search in Google Scholar
  • 16c Reichardt C. J. Prakt. Chem.  1999,  341:  609 
    Search in Google Scholar
  • 16d Gangadasu B. Narender P. Kumar SB. Ravinder M. Rao BA. Ramesh C. Raju BC. Rao VJ. Tetrahedron  2006,  62:  8398 
    Search in Google Scholar
  • 16e Thomas AD. Asokan CV. Tetrahedron  2004,  60:  5069 
    Search in Google Scholar
  • 17a Johnson CR. Lockard JP. Kennedy ER. J. Org. Chem.  1980,  45:  264 
    Search in Google Scholar
  • 17b Zhang Z. Xue C. Liu X. Zhang Q. Liu Q. Tetrahedron  2011,  67:  7081 
    Search in Google Scholar
13

The relative configurations of cis -1k, trans -1l, cis -2k, and trans -2l were determined by NOESY, see Supporting Information.