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DOI: 10.1055/s-0031-1290612
Rh2(OAc)4/CeCl3-Catalyzed Olefination of Carbonylferrocenes with α-Diazocarbonyl Compounds: A Convenient Synthesis of Alkenylferrocenes
Publikationsverlauf
Publikationsdatum:
15. März 2012 (online)

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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References and Notes
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.