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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;
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Publication History

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

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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

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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.