Immobilization of Grubbs Catalyst as Supported Ionic Liquid Catalyst (Ru-SILC)

Abstract

Grubbs olefin metathesis catalyst was immobilized as a ruthenium-supported ionic liquid catalyst (Ru-SILC) in pores of amorphous alumina with the aid of ionic liquid [hmim]PF₆. This Ru-SILC was effective for various olefin metathesis reactions such as intra- or intermolecular macrocyclization and dimerization, and used up to six times after simple decantation.

Key words

heterogeneous catalysis - ionic liquids - methathesis - ruthenium - supported catalysis

References and Notes

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6

Hagiwara, H.; Katsumi, T. unpublished results.

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Preparation of Ru-SILC
To activated Al₂O₃ (powder for column chromatography purchased from Wako Chemical Co., 300 mesh, 1.545 g) and Grubbs I catalyst (1, 38 mg, 0.046 mmol, 0.03 mmol/g of Al₂O₃) was added a solution of [hmim]PF₆ (150 mg, 10 wt%) in THF. The resulting slurry was stirred at r.t. for 4 h, when the pale blue color of THF solution was transferred to Al₂O₃. After evaporation of THF in vacuo, the powder was rinsed with anhyd Et₂O twice. Evacuation in vacuo provided Ru-SILC (1.732 g) as a pale blue powder. Since leaching of Ru into the ether rinse was 0.05 ppm (0.105% as the catalyst 1) by ICP-AES analysis, more than 99% of Grubbs I catalyst(1) was immobilized on Al₂O₃.

21

RCM Reaction of Diethyl Diallylmalonate 4 A stirred suspension of diethyl 2,2-diprop-2-enylpropane-1,3-dioate (4, 31 mg, 0.13 mmol) and Ru-SILC [308 mg, 0.0065 mmol of Grubbs I catalyst(1)] in benzene (1.5 mL) was heated under reflux for 1 h. The organic layer was separated by filtration, and the flask was rinsed with Et₂O. The combined organic layer was evaporated to dryness in vacuo. The residue was purified by medium pressure LC (eluent: n-hexane-EtOAc = 9:1) to give ethyl 1-(ethoxy-carbonyl)cyclopent-3-enecarboxylate (5, 23 mg, 82%). Recovered Ru-SILC was used intact for further recycle experiments.

22

Compound 13: ^¹H NMR (500 MHz, CDCl₃): δ = 1.19-1.47 (m, 20 H), 1.82-2.12 (m, 8 H), 4.13-4.19 (m, 4 H), 5.24-5.33 (m, 1 H), 5.49-5.55 (m, 0.3 H), 5.57-5.63 (m, 0.7 H). ^¹³C NMR (67.5 MHz, CDCl₃): δ = 171.9, 131.5, 130.7, 61.0, 56.5, 31.2, 30.4, 30.3, 28.4, 27.3, 27.0, 26.0, 24.5, 24.2, 20.7, 14.2. MS: m/z (%) = 338 (67) [M⁺], 293 (90), 265 (27), 246 (100), 218 (100), 191 (100), 173 (100), 168 (91). IR: 1723, 1464, 1448, 1368, 1260, 1231, 1190 cm^-¹. HRMS: m/z calcd for C₂₀H₃₄O₄ [M]⁺: 338.2457; found: 338.2458.

23

Compound 17: ^¹H NMR (270 MHz, CDCl₃): δ = 1.21-1.28 (m, 20 H), 1.84-2.00 (m, 16 H), 4.14-4.22 (m, 8 H), 5.39-5.42 (m, 4 H). ^¹³C NMR (67.5 MHz, CDCl₃): δ = 171.7, 130.1, 61.1, 57.0, 32.1, 30.2, 23.5, 14.2. MS: m/z (%) = 536 (7) [M⁺], 491 (13), 444 (8), 399 (15), 336 (19), 279 (8), 265 (16), 251 (12), 173 (100). IR: 1719, 1463, 1445, 1369, 1299, 1254, 1095, 1028 cm^-¹. HRMS: m/z calcd for C₂₈H₄₃O₇ [M - OCH₂CH₃]⁺: 491.3009; found: 491.3017.

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Compound 19: ^¹H NMR (500 MHz, CDCl₃): δ = 1.21-1.34 (m, 14 H), 1.55-1.67 (m, 4 H), 1.73-2.05 (m, 12 H), 2.43-2.60 (m, 4 H), 3.39-3.45 (m, 2 H), 4.14-4.19 (m, 4 H), 5.34-5.42 (m, 4 H). ^¹³C NMR (67.5 MHz, CDCl₃): δ = 205.1, 169.7, 130.3, 129.5, 61.2, 58.3, 41.4, 32.3, 31.8, 28.9, 27.9, 27.4, 23.0, 14.2. MS: m/z (%) = 476 (3) [M⁺], 431 (7), 412 (16), 402 (4), 384 (15), 366 (11), 175 (19), 108 (45), 91 (51), 79 (73), 67 (95), 55 (100). IR: 1738, 1710, 1445, 1370, 1268, 1188, 909 cm^-¹. HRMS: m/z calcd for C₂₆H₃₉O₅ [M - OCH₂CH₃]⁺: 431.2797; found: 431.2802.

25

Compound 21: ^¹H NMR (500 MHz, CDCl₃): δ = 1.25-1.28 (m, 12 H), 1.34-1.41 (m, 4 H), 1.86-1.92 (m, 4 H), 1.99-2.07 (m, 4 H), 3.29-3.33 (m, 2 H), 4.16-4.23 (m, 8 H), 5.34-5.36 (m, 0.6 H), 5.37-5.39 (m, 1.4 H). ^¹³C NMR (67.5 MHz, CDCl₃): δ = 169.3, 129.9, 61.3, 51.9, 32.2, 28.3, 27.3, 14.2. IR: 1726, 1462, 1446, 1371, 1178, 1157 cm^-¹. MS: m/z (%) = 428 (3) [M⁺], 383 (5), 337 (100), 269 (70), 227 (10), 173 (72), 160 (86), 130 (50). HRMS: m/z calcd for C₂₂H₃₆O₈ [M]⁺: 428.2410; found: 428.2394.