Download PDF
Synlett 2012(6): 943-947  
DOI: 10.1055/s-0031-1290612
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Rh2(OAc)4/CeCl3-Catalyzed Olefination of Carbonylferrocenes with α-Diazocarbonyl Compounds: A Convenient Synthesis of Alkenylferrocenes

Shufeng Chen, Lele Zhang, Yan Du, Baoguo Li*
College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, P. R. of China
Fax: +86(471)4992982; e-Mail: bauoguol@sohu.com;
Further Information

Publication History

Received 26 December 2011
Publication Date:
15 March 2012 (online)

    Permissions and Reprints All articles of this category

Abstract

A concise and efficient protocol for the synthesis of al­kenylferrocene derivatives based on the olefination of carbonylferrocenes with α-diazocarbonyl compounds using Rh2(OAc)4/CeCl3 as efficient catalysts was developed. The present method was applicable to many kinds of substituted carbonylferrocenes and α-diazocarbonyl compounds providing good to excellent yields of desired products.

Key words

carbonylferrocenes - diazo compounds - olefination - alkenylferrocene

    References and Notes

  • 1a Togni A. Hayashi T. Ferrocenes   VCH; New York: 1995. 
    Google Scholar
  • 1b Atkinson RCJ. Gibson VC. Long NJ. Chem. Soc. Rev.  2004,  33:  213 
    Google Scholar
  • 2a Green MLH. Marder SR. Thompson ME. Bandy JA. Bloor D. Kolinsky PV. Jones RJ. Nature (London)  1987,  330:  360 
    Google Scholar
  • 2b Togni A. Angew. Chem., Int. Ed. Engl.  1996,  35:  1475 
    Google Scholar
  • 2c Richards CJ. Locke AJ. Tetrahedron: Asymmetry  1998,  9:  2377 
    Google Scholar
  • 2d Dai LX. Tu T. You SL. Deng WP. Hou XL. Acc. Chem. Res.  2003,  36:  659 
    Google Scholar
  • 2e Thomas JC. Chem. Rev.  2003,  103:  3101 
    Google Scholar
  • 2f Arrayas RG. Adrido J. Carretero JC. Angew. Chem. Int. Ed.  2006,  45:  7674 
    Google Scholar
  • 2g Moyano A. Rios R. Synlett  2009,  1863 
    Google Scholar
  • 2h Sondenecker A. Cvengros J. Aardoom R. Togni A. Eur. J. Org. Chem.  2011,  78 
    Google Scholar
  • 3a Barlow S. Marder SR. In Functional Organic Materials   Müller TJJ. Bunz UHF. Wiley-VCH; Weinheim: 2007.  p.393-437  
    Google Scholar
  • 3b Kato S.-i. Beels MTR. La Porta P. Schweizer WB. Boudon C. Gisselbrecht J.-P. Biaggio I. Diederich F. Angew. Chem. Int. Ed.  2010,  49:  6207 
    Google Scholar
  • 4a Hudson SA. Maitlis PM. Chem. Rev.  1993,  93:  861 
    Google Scholar
  • 4b Ferrocenes: Homogenous Catalysis. Organic Synthesis. Materials Science   Togni A. Hayshi T. VCH; Weinheim: 1995. 
    Google Scholar
  • 4c Long NJ. Metallocenes   1st. ed.:  Blackwell Science; London: 1997. 
    Google Scholar
  • 4d Sutclie OB. Bryce MR. Tetrahedron: Asymmetry  2003,  14:  2297 
    Google Scholar
  • 4e Kadkin ON. Han H. Galyametdinov YG. J. Organomet. Chem.  2007,  692:  5571 
    Google Scholar
  • 4f Ochi Y. Suzuki M. Imaoka T. Murata M. Nishihara H. Einaga Y. Yamamoto K. J. Am. Chem. Soc.  2010,  132:  5061 
    Google Scholar
  • 5a Molina P. Pastor A. Vilaplana MJ. Velasco MD. Ramirez de Arellano MC. Organometallics  1997,  16:  5836 
    Google Scholar
  • 5b Molina P. Tarraga A. Lopez JL. Martinez JC. J. Organomet. Chem.  1999,  584:  147 
    Google Scholar
  • 5c Bollo S. Vergara LJ. Bonta M. Chauviere G. Perie J. Squella JA. Electroanal. Chem.  2001,  511:  46 
    Google Scholar
  • 5d Van Staveren DR. Metzler-Nolte N. Chem. Rev.  2004,  104:  5931 
    Google Scholar
  • 5e Fouda MFR. Abd-Elzaher MM. Abdelsamaia RA. Labib AA. Appl. Organomet. Chem.  2007,  21:  613 
    Google Scholar
  • 5f Buriez O. Heldt JM. Labbe E. Vessieres A. Jaouen G. Amatore C. Chem. Eur. J.  2008,  14:  8195 
    Google Scholar
  • 5g Metzler-Nolte N. Salmain M. In Ferrocenes: Ligands, Materials and Biomolecules   Stepnicka P. Wiley; New York: 2008.  p.499 
    Google Scholar
  • 5h Patra M. Gasser G. Wenzel M. Merz K. Bandow JE. Metzler-Nolte N. Organometallics  2010,  29:  4312 
    Google Scholar
  • 6 Debroy P. Roy S. Coord. Chem. Rev.  2007,  251:  203 
    Google Scholar
  • 7a Rodriguez J.-G. Gayo M. Fonseca I. J. Organomet. Chem.  1997,  534:  35 
    Google Scholar
  • 7b Thomas KRJ. Lin JT. Wen YS. J. Organomet. Chem.  1999,  575:  301 
    Google Scholar
  • 7c Mata JA. Falomir E. Llusar R. Peris E. J. Organomet. Chem.  2000,  616:  80 
    Google Scholar
  • 7d Mata JA. Uriel S. Llusar R. Peris E. Organometallics  2000,  19:  3797 
    Google Scholar
  • 8a Hradsky A. Bildstein B. Schuler N. Schottenberger H. Jaitner P. Ongania K.-H. Wurst K. Launay J.-P. Organometallics  1997,  16:  392 
    Google Scholar
  • 8b Chesney A. Bryce MR. Batsanov AS. Howard JAK. Goldenberg LM. Chem. Commun.  1998,  677 
    Google Scholar
  • 8c Stepnicka P. Lamac M. Cisarova I. J. Organomet. Chem.  2008,  693:  446 
    Google Scholar
  • 8d Granzhan A. Teulade-Fichou M.-P. Tetrahedron  2009,  65:  1349 
    Google Scholar
  • 9 Blakemore PR. Ho DKH. Nap WM. Org. Biomol. Chem.  2005,  3:  1365 
    Google Scholar
  • 10 Jary WG. Mahler A.-K. Purkathofer T. Baumgartner J. J. Organomet. Chem.  2001,  629:  208 
    Google Scholar
  • 11a Kasahara A. Izumi T. Maemura M. Bull. Chem. Soc. Jpn.  1977,  50:  1021 
    Google Scholar
  • 11b Naskar D. Das SK. Giribabu L. Maiya BG. Roy S. Organometallics  2000,  19:  1464 
    Google Scholar
  • 11c Kundu A. Prabhakar S. Vairamani M. Roy S. Organometallics  1997,  16:  4796 
    Google Scholar
  • 11d Jong S.-J. Fang J.-M. J. Org. Chem.  2001,  66:  3533 
    Google Scholar
  • 11e Sinha P. Roy S. Chem. Commun.  2001,  1798 
    Google Scholar
  • 11f Debroy P. Roy S. J. Organomet. Chem.  2003,  675:  105 
    Google Scholar
  • For comprehensive reviews about transition-metal-catalyzed olefinations of aldehydes or ketones with diazo compounds, see:
  • 12a Doyle MP. McKervey MA. Ye T. Modern Catalytic Methods for Organic Synthesis with Diazo Compounds   Wiley-Interscience; New York: 1998. 
    Google Scholar
  • 12b Herrmann WA. Olefins from Aldehydes in Applied Homogeneous Catalysis with Organometallic Compounds   2nd ed., Vol. 3:  Wiley-VCH; Weinheim: 2002.  p.1078-1086  
    Google Scholar
  • 12c Zhang Z. Wang J. Tetrahedron  2008,  64:  6577 
    Google Scholar
13

General Procedure
To a solution of carbonylferrocenes 1a-f (0.3 mmol), Ph3P (0.33 mmol), CeCl3 (0.15 mmol), and Rh2 (OAc)4 (0.5 mmol%) in anhyd DCE (3 mL) at 80 ˚C was added dropwise a solution of individual diazo compounds 2a-h (0.45 mmol) in anhyd DCE (2 mL). The progress of the reaction was monitored by TLC. After completion of the reaction, solvent was removed by evaporation, and the residue was purified by column chromatography over silica gel to give the olefination products 3a-f and 4a-g.
Representative Spectroscopic Data
Compound 3f: purple solid; mp 76-77 ˚C. IR (KBr): 3103, 3037, 1713, 1614, 1583, 1291, 1168, 1038, 1002 cm-¹. ¹H NMR (500 MHz, CDCl3): δ = 1.40 (t, J = 7.0 Hz, 3 H), 4.22 (s, 5 H), 4.40 (q, J = 7.0 Hz, 2 H), 4.51 (t, J = 1.5 Hz, 2 H), 4.73 (t, J = 1.5 Hz, 2 H), 6.77 (d, J = 9.5 Hz, 1 H), 7.88 (s, 1 H), 8.81 (d, J = 9.5 Hz, 1 H). ¹³C NMR (125 MHz, CDCl3): δ = 14.2, 62.0, 68.4, 68.6, 70.5, 71.6, 81.5, 116.8, 149.4, 151.3, 163.3, 164.7. Anal. Calcd for C17H17ClFeO2: C, 59.25; H, 4.97. Found: C, 58.90; H, 5.17.
Compound 4e: purple solid; mp 127-129 ˚C. IR (KBr): 3105, 1733, 1617, 1521, 1347, 1221, 1039 cm-¹. ¹H NMR (500 MHz, CDCl3): δ = 4.01 (s, 3 H), 4.24 (s, 5 H), 4.55 (s, 2 H), 4.74 (s, 2 H), 7.96 (d, J = 5.0 Hz, 2 H), 8.28 (d, J = 5.0 Hz, 2 H), 8.59 (s, 1 H). ¹³C NMR (125 MHz, CDCl3): δ = 52.2, 69.6, 69.7, 72.1, 72.4, 124.0, 128.0, 137.9, 149.0, 157.0, 165.6, 166.2. Anal. Calcd for C20H17FeNO4: C, 61.40; H, 4.38; N, 3.58. Found: C, 60.11; H, 4.70; N, 3.79.