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DOI: 10.1055/s-2008-1077888
Synthesis of Imidazolium-Tagged Ruthenium Carbene Complex: Remarkable Activity and Reusability in Regard to Olefin Metathesis in Ionic Liquids
Publication History
Publication Date:
19 June 2008 (online)
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Abstract
We have demonstrated the synthesis of a new ionic liquid supported ruthenium carbene complex 1a,b and its applications to olefin metathesis. These catalysts can be used for ring-closing metathesis in the construction of five-to-eight-membered rings with high activity and good recyclability.
Keywords
ruthenium - catalysis - metathesis - ionic liquids - carbene complexes
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References and Notes
Procedure for
the Synthesis of Catalyst 1b
To a solution of 9 (184.9 mg, 0.22 mmol) and CuCl (21.6 mg,
0.22 mmol) in CH2Cl2 (20 mL) was added 8b (120.3 mg, 0.26 mmol). The reaction
mixture was stirred at reflux for 9 h under argon atmosphere. The
volatiles were removed under reduce pressure. The residue was purified
by column chromatography on SiO2 (CH2Cl2-acetone,
3:1) to afford 1b (137.2 mg, 68%). ¹H
NMR (400 MHz, CD2Cl2): δ = 1.14
(d, J = 6.3
Hz, 6 H), 1.66-1.74 (m, 2 H), 1.89-1.94 (m, 2
H), 2.20-2.65 (br, 18 H), 3.72 (s, 3 H), 4.06 (t, J = 5.7 Hz,
2 H), 4.08 (t, J = 6.9
Hz, 2 H), 4.16 (s, 4 H), 5.64 (sept, J = 6.3
Hz, 1 H), 6.56 (dd, J = 1.3,
7.5 Hz, 1 H), 6.87 (dd, J = 7.5,
8.2 Hz, 1 H), 7.06 (br, 4 H), 7.11 (dd, J = 1.3,
8.2 Hz, 1 H), 7.13 (dd, J = 1.9,
1.9 Hz, 1 H), 7.25 (dd, J = 1.3,
1.9 Hz, 1 H), 8.48 (br, 1 H), 16.57 (s, 1 H). ¹³C
NMR (100 MHz, CD2Cl2): δ = 19.6,
21.2, 21.7, 25.4, 26.9, 36.6, 49.9, 51.8, 68.8, 81.0, 115.9, 122.7,
123.9, 124.3, 129.6, 136.0, 136.1, 138.5, 139.3, 140.3, 148.3, 148.6,
210.0, 298.3. IR (KBr): ν = 1574 (w), 1470 (m),
1269 (m) cm-¹. HRMS-FAB: m/z calcd
for C39H51
³5Cl2N4O2
¹0²Ru:
779.2433; found: 779.2454. Anal. Calcd for C39H51Cl2F6N4O2PRu:
C, 50.65; H, 5.56; N, 6.06. Found: C, 50.62; H, 5.58; N, 5.82.
Typical Procedure
for Metathesis Reaction Promoted by Ionic Liquid Supported Ruthenium
Catalyst
To a catalyst solution of 1b (38.1
mg, 0.04 mmol) in [Bmim]PF6 (1 mL)
was added 10 (0.20 mL, 0.82 mmol) in CH2Cl2 (9
mL). The reaction mixture was stirred at r.t. until starting material
was consumed. After the volatiles were removed under reduce pressure,
ionic liquid phase was extracted with Et2O (several times).
The ethereal phase was evaporated to provide 11,
and the ionic liquid phase was dried under reduce pressure to use
a catalyst solution for the next cycle.