Synlett 2015; 26(09): 1191-1194
DOI: 10.1055/s-0034-1380510
letter
© Georg Thieme Verlag Stuttgart · New York

Ionophilic Imidazolium-Tagged Cinchona Ligand on LDH-Immobilized Osmium: Recyclable and Recoverable Catalytic System for Asymmetric Dihydroxylation Reaction of Olefins

Amanpreet Kaur
Department of Applied Sciences (Chemistry), PEC University of Technology, Sector-12, Chandigarh 160012, India   Email: vasun7@yahoo.co.in
,
Vasundhara Singh*
Department of Applied Sciences (Chemistry), PEC University of Technology, Sector-12, Chandigarh 160012, India   Email: vasun7@yahoo.co.in
› Author Affiliations
Further Information

Publication History

Received: 05 December 2014

Accepted after revision: 05 March 2015

Publication Date:
30 March 2015 (online)


Abstract

A catalytic system for the asymmetric dihydroxylation of olefins was developed by using an ionic-tagged biscinchona alkaloid ligand immobilized onto OsO4-exchanged layered double hydroxide (LDH) as a robust recyclable homogenous–heterogeneous catalytic system. The desired products were obtained in high yield and enantioselectivity.

Supporting Information

 
  • References and Notes

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  • 18 Compound 5 1H NMR (400 MHz, CDCl3): δ = 1.36–1.44 (m, 2 H, NCH2CH2CH 2CH2CH2 imidazolium), 1.48–1.53 (m, 2 H, quinuclidine H), 1.74–1.88 (m, 10 H, quinuclidine H), 1.91–1.99 (m, 4 H, N+CH2CH2CH 2CH 2CH2CH2 imidazolium), 2.04–2.13 (m, 4 H, N+CH2CH 2CH2CH2CH 2CH2 imidazolium), 2.13–2.17 (m, 2 H, quinuclidine H), 2.68–2.78 (m, 2 H, quinuclidine H), 2.80–2.91 (m, 2 H, quinuclidine H), 3.15–3.18 (m, 2 H, quinuclidine H), 3.38–3.48 (m, 2 H, quinuclidine H), 3.54 (t, 2 H, J = 6.4 Hz, N+CH 2CH2CH2CH2CH2CH2 imidazolium), 3.93 (s, 6 H, OCH3), 4.01 (s, 3 H, NCH3), 4.35 (t, 2 H, J = 7.4 Hz, CH2CH 2 imidazolium), 5.02–5.17 (m, 4 H, CH 2=CH), 5.52–5.56 (m, 2 H, CH2=CH), 7.28 (d, 1 H, J = 2.7 Hz, CHO), 7.30 (d, 1 H, J = 2.7 Hz, CHO), 7.31 (s, 1 H, imidazolium H), 7.32–7.39 (m, 2 H, phthalazine H), 7.45 (d, 2 H, J = 1.8 Hz, imidazolium H), 7.50–7.52 (m, 2 H, 2 x quinolyl H), 7.81–7.83 (m, 2 H, phthalazine H), 7.91–7.93 (m, 2 H, 2 × quinolyl H), 8.08 (d, 2 H, J = 8.5 Hz, 2 × quinolyl H), 8.31–8.35 (m, 2 H, quinolyl H), 8.72 (d, 1 H, J = 4.8 Hz, quinolyl H), 8.78 (d, 1 H, J = 4.6 Hz, quinolyl H). 13C NMR (400 MHz, CDCl3): δ = 157.3, 145.8, 143.5, 142.7, 142.4, 136.2, 136.0, 130.1, 124.4, 122.3, 121.7, 121.3, 118.0, 116.4, 116.2, 99.1, 65.5, 65.0, 63.4, 59.1, 56.3, 55.4, 55.1, 53.7, 52.6, 43.1, 36.6, 36.0, 35.6, 29.9, 28.6, 28.2, 25.9, 25.2, 24.2, 23.7, 23.2, 21.2, 17.1. MS (ES+): m/z (%) = 945.1 (20) [M + H]+, 325.5 (100) [M – C38H48N6O2]+.
  • 19 Typical Procedure for Assymetric Dihydroxylation of trans-Stilbene Using Catalyst 5 LDH-OsO4 (0.020 g, 0.017 mmol), [(QN)2PHAL-C5mim]Br (5, 0.0102 g, 0.01 mmol) in [bmim]PF6–H2O–acetone (0.1:1:8, v/v) was stirred at 0 °C for 15–20 min. To this was added NMO (0.200 g, 5.13 mmol) and subsequently trans-stilbene (0.103g, 1.7 mmol) over a period of 10 h at r.t. After completion of reaction as indicated by TLC, the volatiles were removed under vacuum and Et2O was added to the reaction mixture. The ether layer was separated, and the procedure was repeated thrice (3 × 10 mL). The combined ether layer was washed with water, brine, and dried over anhydrous Na2SO4. After evaporating the solvent, the crude product was vacuum dried. Column chromatography of the crude on silica gel (EtOAc–hexane, 2:8) gave the desired diol in 96% yield.
  • 20 HPLC Analysis (Table 3) Entry 1 (diol): Daicel Chiralcel OJ, hexane–i-PrOH (4:1), flow rate 0.6 mL/min, t R (min) = 11.7 (minor), 13.7 (major). Entry 2 (diol): Daicel Chiralcel OD-H, hexane–i-PrOH (19:1), flow rate 0.5 mL/min, t R = 43.99 (major), t R = 48.73 (minor). Entry 3 (diol): Daicel Chiralcel OD-H, hexane–i-PrOH (5.6:1), flow rate 1.0 mL/min, t R (min) = 5.5 (major), 8.0 (minor). Entry 4 (diol): Daicel Chiralcel OJ, hexane–i-PrOH (5.6:1), flow rate 1.0 mL/min, t R (min) = 6.5 (minor), 7.6 (major). Entry 5 (diol): Daicel Chiralcel OD-H, hexane–i-PrOH (7.5:2.5), flow rate 1.0 mL/min, t R (min) = 2.5 (minor), 5.7 (major). Entry (diol): Daicel Chiralcel OD-H, hexane–i-PrOH (9.5:0.5), flow rate 1.0 mL/min, t R (min) = 4.6 (minor), 9.3 (major).
  • 21 Choi DS, Han SS, Kwueon EK, Choi HY, Hwang SH, Park YS, Choung ES. Adv. Synth. Catal. 2006; 348: 2560
  • 22 Typical Procedure for Recycling of trans-Stilbene Using Catalyst 5 LDH-OsO4 (0.01 g, 0.005 mmol) was added to the remaining catalytic system, after extraction of the product and was stirred at 0 °C for 15–20 min. To this was added fresh dose of NMO (0.200 g, 5.13 mmol) and subsequently trans-stilbene (0.103 g, 1.7 mmol) over a period of 10 h at r.t. After completion of reaction as indicated by TLC, the volatiles were removed under vacuum, and Et2O was added to the reaction mixture. The ether layer was separated, and the procedure was repeated thrice (3 × 10 mL). The combined ether layer was washed with H2O and brine, and dried over anhydrous Na2SO4. After evaporating the solvent, the crude product was vacuum dried. Column chromatography of the crude on silica gel (EtOAc–hexane, 2:8) gave the desired diol in 95.5% yield.