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DOI: 10.1055/s-2005-864807
Cp2ZrCl2-Mediated Three-Component Coupling Reactions of CO2, Ethylene (or Alkynes), and Electrophiles Leading to Carboxylic Acid Derivatives
Publication History
Publication Date:
23 March 2005 (online)
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Abstract
Zirconacycles 1 and 2 can be simply generated from Cp2ZrCl2, EtMgBr, and an atmospheric pressure of CO2. The treatment of Cp2ZrCl2 with EtMgBr followed by exposure to CO2 generates zirconacycle 1, which can react with various electrophiles to give a variety of carboxylic acid derivatives. Unsaturated zirconacycles 2 can also generated from Cp2ZrCl2, EtMgBr, alkynes, and CO2. Complexes 2 react with electrophiles to give α,β-unsaturated acids stereoselectively.
Key words
carbon dioxide - carboxylic acids - Grignard reactions - metallacycles - nucleophilic additions - alkynes
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References
The reaction was carried out in a 20 mL two-necked flask equipped with a condenser and an inlet tube. To a solution of Cp2ZrCl2 (1 mmol, 292 mg) in THF (10 mL) under an atmosphere of dry nitrogen was added EtMgBr (3.0 M solution in Et2O, 2.2 mmol, 740 µL) at -78 °C. After the mixture was stirred for 1 h at the same temperature, carbon dioxide was bubbled from CO2 balloon and the reaction mixture was allowed to warm to 0 °C. After the mixture was stirred for 30 min, CuI (1.2 mmol, 228.6 mg) and allyl bromide (1.2 mmol) was added to the reaction mixture, which was stirred at 60 °C for 12 h. Then, the reaction mixture was quenched with 1 N HCl and extracted with Et2O. The organic layer was extracted with 4 N NaOH aq and the aqueous layer was neutralized with 6 N HCl, washed with Et2O and brine, dried over MgSO4. A crude product was obtained after evaporation of the residue in vacuo.
5-Bromohex-5-enoic Acid (4): colorless oil. 1H NMR (CDCl3): δ = 1.91 (tt, J = 7.3, 7.3 Hz, 2 H, CH2), 2.39 (t, J = 7.3 Hz, 2 H, CH2CO), 2.49 (t, J = 7.3 Hz, 2 H, CH2C=), 5.44 (d, J = 1.9 Hz, 1 H, CH=), 5.60-5.61 (m, 1 H, CH=). 13C NMR (CDCl3): δ = 22.6 (CH2), 32.3 (CH2CO), 40.3 (CH2C=), 117.6 (CH2=), 133.1 (C=), 179.6 (CO). IR (neat): 2944 (s), 2913 (s), 2753 (m), 2670 (m), 1720 (s), 1704 (s), 1629 (s), 1452 (s), 1430 (s), 1411 (s), 1245 (s), 1201 (s), 1180 (s), 1118 (s), 1060 (w), 1035 (w), 1002 (w), 925 (s), 890 (s), 779 (m), 644 (w), 605 (w), 555 (w), 532 (m). MS: m/z calcd for C6H1081BrO2: 194.9844; found: 194.9859.
The reaction was carried out in a 20 mL two-necked flask equipped with a condenser and a three-way cock. To a solution of Cp2ZrCl2 (1 mmol, 292.3 mg) in THF (10 mL) under an atmosphere of dry nitrogen was added EtMgBr (3.0 M solution in Et2O, 2.2 mmol, 740 µL) at -78 °C. After the mixture was stirred for 1 h at the same temperature reaction mixture was allowed to warm to 0 °C, and alkyne (1.0 mmol) was added. After the mixture was stirred, the flask was changed with CO2 and warmed to 50 °C. After the mixture was stirred for 1 h, the reaction mixture was quenched with 1 N HCl and extracted with Et2O. The organic layer was extracted with 4 N NaOH aq and aqueous layer was neutralized with 6 N HCl, washed with Et2O and brine, dried over MgSO4. The solvent was evaporated in vacuo and afforded products.
2,3-Diethylhexa-2,5-dienoic Acid (13): colorless oil. 1H NMR (CDCl3): δ = 1.05 (t, J = 7.6 Hz, 3 H, CH3), 1.06 (t, J = 7.6 Hz, 3 H, CH3), 2.16 (q, J = 7.6 Hz, 2 H, CH2), 2.35 (q, J = 7.6 Hz, 2 H, CH2), 3.17 (d, J = 6.6 Hz, 1 H, =CCH2C=), 5.01 (dd, J = 8.5, 1.9 Hz, 1 H, CH2=), 5.06 (dd, J = 15.4, 1.9 Hz, 1 H, CH2=), 5.75-5.90 (m, 1 H, CH=). 13C NMR (CDCl3): δ = 12.8 (CH3), 14.1 (CH3), 22.8 (CH2), 26.3 (CH2), 38.4 (=CCH2C=), 115.8 (CH2=), 129.2 (COC=), 136.1 (CH=), 151.6 (C=), 174.5 (CO). IR (neat): 3077 (s), 2971 (s), 2935 (s), 2877 (s), 1681 (s), 1637 (s), 1617 (s), 1455 (m), 1403 (s), 1376 (m), 1301 (s), 1251 (s), 1191 (s), 1122 (w), 1049 (w), 997 (m), 948 (m), 912 (s), 788 (m), 746 (w) cm-1. MS: m/z calcd for C10H16O2: 168.1150; found: 168.1157.