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Enantioselective Friedel-Crafts reaction with ethyl 2,2,2- trifluoropyruvate: (a) Zhuang, W.; Gatherwood, N.; Hazell, R. G.; Jørgensen, K. A. J. Org. Chem. 2001, 66, 1009.
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Enantioselective Friedel-Crafts reaction with ethyl 2,2,2- trifluoropyruvate: (a) Zhuang, W.; Gatherwood, N.; Hazell, R. G.; Jørgensen, K. A. J. Org. Chem. 2001, 66, 1009.
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Enantioselective carbonyl-ene reaction: Aikawa, K.; Kainuma, S.; Manabu, H.; Mikami, K. Tetrahedron Lett. 2004, 45, 183.
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(d) Enantioselective carbonyl-ene reaction: Aikawa, K.; Kainuma, S.; Manabu, H.; Mikami, K. Tetrahedron Lett. 2004, 45, 183.
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19
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34548808040
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19F NMR spectroscopic analysis with benzotrifluoride as internal standard (δ = -61.5 ppm).
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19F NMR spectroscopic analysis with benzotrifluoride as internal standard (δ = -61.5 ppm).
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20
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0033105506
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For a practical example, see: a, 711. Other examples include
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For a practical example, see: (a) Tan, L.; Chen, C.-y.; Tillyer, R. D.; Grabowski, E. J. J.; Reider, P. J. Angew. Chem. Int. Ed. 1999, 38, 711. Other examples include:
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(d) Abenhaim, D.; Boireau, G.; Sabourault, B. Tetrahedron Lett. 1980, 21, 3043.
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24
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For reviews on the use of BINOL in asymmetric synthesis, see: a
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For reviews on the use of BINOL in asymmetric synthesis, see: (a) Brunei, J. M. Chem. Rev. 2005, 105, 857.
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A similar BINOL-derived zincate species has been reported as a Lewis acid catalyst for enantioselective Diels-Alder cycloadditions: Ward, D. E, Souweha, M. S. Org. Lett. 2005, 7, 3533
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A similar BINOL-derived zincate species has been reported as a Lewis acid catalyst for enantioselective Diels-Alder cycloadditions: Ward, D. E.; Souweha, M. S. Org. Lett. 2005, 7, 3533.
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Experimental Procedure (R, )-1,1′-Bi(2-naphthol)(5. 1 g, 17.6 mmol, 120 mol, was dissolved in anhyd 1,2-dichloroethane (35 mL) and THF (8.75 mL) and the solution was cooled to -40°C. A solution of Et 2Zn (13.4 mL, 14.7 mmol, 100 mol, 1.1 M in toluene) was added over 30 min. Caution: gas evolution! Proper venting required! The mixture was stirred at r.t. for 1 h, cooled to -40°C and a solution of EtMgCl (8.8 mL, 17.6 mmol, 120 mol, 2 M in THF) was added over 15 min. The solution was warmed to r.t. for 1 h and then cooled to -40°C. Ethyl 2,2,2-trifluoropyruvate (1.95 mL, 2.50 g, 14.7 mmol) was added dropwise via syringe pump over 6 h. The mixture was let stir 18 h and then quenched with 2 N aq HCl (25 mL, The organic layer was washed with 1 N aq NaOH (3 x 20 mL, The organic layer was then treated with 8 N KOH 200 mol, at reflux for 2 h. The solution was cooled to r.t. and the layers were separated. The aqueous layer was washed wi
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3 at -61.5 ppm): δ = -77.3. Chiral GC analysis (methyl ester): Cyclodex-B column, 50°C for 1 min, 5°C/min to 95°C, hold at 95°C for 1 min, 20°C/min to 200°C, injector 180°C, detector 250°C, split 10:1, 13.5 psi He, S-enantiomer at 6.10 min, R-enantiomer at 6.83 min.
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