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3CK: House, H. O.; Kramar, V. J. Org. Chem. 1963, 28, 3362.
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3CK: House, H. O.; Trost, B. M. J. Org. Chem. 1965, 30, 1341.
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7
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0019408557
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MesLi: Woodward, R. B.; Logusch, E.; Nambiar, K. P.; Sakan, K.; Ward, D. E.; Au-Yeung, B.-W.; Balaram, P.; Browne, L. J.; Card, P. J.; Chen, C. H.; Chênevert, R. B.; Fliri, A.; Frobel, K.; Gais, H.-J.; Garratt, D. G.; Hayakawa, K.; Heggie, W.; Hesson, D. P.; Hoppe, D.; Hoppe, I.; Hyatt, J. A.; Ikeda, D.; Jacobi, P. A.; Kim, K. S.; Kobuke, Y.; Kojima, K.; Krowicki, K.; Lee, V. J.; Leutert, T.; Machenko, S.; Martens, J.; Matthews, R. S.; Ong, B. S.; Press, J. B.; Rajan Babu, T. V.; Rousseau, G.; Sauter, H. M.; Suzuki, M.; Tatsuta, K.; Tolbert, L. M.; Truesdale, E. A.; Uchida, I.; Ueda, Y.; Uyehara, T.; Vasella, A. T.; Vladuchick, W. C.; Wade, P. A.; Williams, R. M.; Wong, H. N.-C. J. Am. Chem. Soc. 1981, 103, 3210.
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(d) MesLi: Woodward, R. B.; Logusch, E.; Nambiar, K. P.; Sakan, K.; Ward, D. E.; Au-Yeung, B.-W.; Balaram, P.; Browne, L. J.; Card, P. J.; Chen, C. H.; Chênevert, R. B.; Fliri, A.; Frobel, K.; Gais, H.-J.; Garratt, D. G.; Hayakawa, K.; Heggie, W.; Hesson, D. P.; Hoppe, D.; Hoppe, I.; Hyatt, J. A.; Ikeda, D.; Jacobi, P. A.; Kim, K. S.; Kobuke, Y.; Kojima, K.; Krowicki, K.; Lee, V. J.; Leutert, T.; Machenko, S.; Martens, J.; Matthews, R. S.; Ong, B. S.; Press, J. B.; Rajan Babu, T. V.; Rousseau, G.; Sauter, H. M.; Suzuki, M.; Tatsuta, K.; Tolbert, L. M.; Truesdale, E. A.; Uchida, I.; Ueda, Y.; Uyehara, T.; Vasella, A. T.; Vladuchick, W. C.; Wade, P. A.; Williams, R. M.; Wong, H. N.-C. J. Am. Chem. Soc. 1981, 103, 3210.
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3: Seebach, D.; Erta̧s, M.; Locher, R.; Schweizer, W. B. Helv. Chim. Acta 1985, 68, 264.
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3: Ertas, M.; Seebach, D. Helv. Chim. Acta 1985, 68, 961.
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2442610761
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For both the efficacy and issues with reagents such as the commonly used lithium-based amides, see: a, Paquette, L. A, Ed, Wiley: Chichester
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For both the efficacy and issues with reagents such as the commonly used lithium-based amides, see: (a) Bakker, W. I. I.; Wong, P. L.; Snieckus, V. In Encyclopedia of Reagents for Organic Synthesis, Vol. 5; Paquette, L. A., Ed.; Wiley: Chichester, 1995, 3096.
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Bakker, W.I.I.1
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Scheffold, R, Ed, Wiley-VCH: New York
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Trost, B. M, Fleming, I, Eds, Pergamon: Oxford
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(c) Caine, D. In Comprehensive Organic Synthesis, Vol. 3; Trost, B. M.; Fleming, I., Eds.; Pergamon: Oxford, 1991, 1.
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(d) Kowalski, C.; Creary, X.; Rollin, A. J.; Burke, M. C. J. Org. Chem. 1978, 43, 2601.
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14
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45849099451
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For example, n-BuLi will deliver mostly addition products when used in a general sense with ketones. Only in specific cases will n-BuLi act solely as a base reagent. For general information on the reactivity of n-BuLi, see: (a) Brandsma, L.; Verkruijsse, H. D. Preparative Polar Organometallic Chemistry; Springer: Berlin, 1987.
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For example, n-BuLi will deliver mostly addition products when used in a general sense with ketones. Only in specific cases will n-BuLi act solely as a base reagent. For general information on the reactivity of n-BuLi, see: (a) Brandsma, L.; Verkruijsse, H. D. Preparative Polar Organometallic Chemistry; Springer: Berlin, 1987.
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16
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45849086890
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For the use of base reagent mixtures with n-BuLi, see ref. 2e and 2f.
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(c) For the use of base reagent mixtures with n-BuLi, see ref. 2e and 2f.
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17
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45849088044
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1.5 mol of the complex (i.e., 4.5 equiv of base) was required at 125°C
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3 to perform effectively in deprotonation reactions
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3 to perform effectively in deprotonation reactions, 1.5 mol of the complex (i.e., 4.5 equiv of base) was required at 125°C; see ref. 1a.
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19
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0842328402
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Dinsmore, A.; Billing, D. G.; Mandy, K.; Michael, J. P.; Mogano, D.; Patil, S. Org. Lett. 2004, 6, 293.
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(a) Starowieyski, K. B.; Lewinski, J.; Wozniak, R.; Chrost, A. Organometallics 2003, 22, 2458.
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(a) Bassindale, M. J.; Crawford, J. J.; Henderson, K. W.; Kerr, W. J. Tetrahedron Lett. 2004, 45, 4175.
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Bassindale, M.J.1
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0038237115
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(b) Carswell, E. L.; Hayes, D.; Henderson, K. W.; Kerr, W. J.; Russell, C. J. Synlett 2003, 1017.
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Carswell, E.L.1
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0037013928
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(c) Henderson, K. W.; Kerr, W. J.; Moir, J. H. Tetrahedron 2002, 58, 4573.
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Henderson, K.W.1
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Moir, J.H.3
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0035479678
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(d) Anderson, J. D.; García García, P.; Hayes, D.; Henderson, K. W.; Kerr, W. J.; Moir, J. H.; Fondekar, K. P. Tetrahedron Lett. 2001, 42, 7111.
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Anderson, J.D.1
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Kerr, W.J.5
Moir, J.H.6
Fondekar, K.P.7
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45849116887
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Typical Experimental Procedure for the Deprotonation of Ketones Using (Isolated) t-Bu2Mg A Schlenk tube was charged with LiCl (1 mmol, 42.5 mg) and flame-dried under vacuum. The tube was purged three times with N2 before being cooled to r.t. and charged with t-Bu2Mg (0.5 M solution in THF, 0.5 mmol, 1 mL) and THF (9 mL, The mixture was stirred for 15 min at r.t. before being cooled to 0°C. Then, TMSCl (1 mmol, 109 mg, 0.13 mL) was added and the mixture was stirred for 5 min before addition of cyclohexanone (2a, 1 mmol, 98 mg) as a solution in THF (2 mL) over 1 h via syringe pump. The reaction mixture was stirred at 0°C under N2 for 1 h before being quenched with sat. aq NaHCO3 solution (10 mL, The mixture was allowed to warm to r.t. before being extracted with Et2O (1 x 40 mL and 2 x 25 mL, The combined organic extracts were dried (Na2SO4) and a repres
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-1; (iv) final oven temperature, 190°C; and (v) detection method, FID.
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30
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0003495414
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For the preparation of dialkylmagnesium reagents using 1,4-dioxane, see:, Academic Press: London
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For the preparation of dialkylmagnesium reagents using 1,4-dioxane, see: Wakefield, B. J. Organomagnesium Methods in Organic Synthesis; Academic Press: London, 1995.
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(1995)
Organomagnesium Methods in Organic Synthesis
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Wakefield, B.J.1
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31
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45849120959
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Typical Experimental Procedure for the Deprotonation of Ketones Using in situ Generated t-Bu2Mg A Schlenktube was charged with LiCl (1 mmol, 85 mg) and flame-dried under vacuum. The tube was purged three times with N2 before being cooled to r.t. and charged with t-BuMgCl (1 M solution in THF, 1 mmol, 1 mL, 1,4-dioxane (1.05 mmol, 88 mg, 0.09 mL, and THF (9 mL, The mixture was stirred for 15 min at r.t. before being cooled to 0°C. Then, TMSCl (1 mmol, 109 mg, 0.13 mL) was added and the mixture was stirred for 5 min before addition of 1,4-cyclohexanedione monoethylene ketal (2i, 1 mmol, 156 mg) as a solution in THF (2 mL) over 1 h via syringe pump. The reaction mixture was stirred at 0°C under N2 for 1 h before being quenched with sat. NaHCO3 aq soin (10 mL, The mixture was allowed to warm to r.t. before being extracted with Et2O 1 x 40 mL and 2 x 25 mL, The combined organic extracts
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32
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45849148057
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Product Data 1-Trimethylsilyloxycyclohexene (3a, 14,15,16a,17 IR (CH2Cl2, νmax, 1668 cm-1. 1H NMR (400 MHz, CDCl3, δ, 0.18 [s, 9 H, Si(CH3)3, 1.48-1.54 (m, 2 H, CH 2, 1.63-1.69 (m, 2 H, CH2, 1.97-2.03 (m, 4 H, 2 x CH2, 4.86-4.88 (m, 1 H, CH, 1-Trimethylsiloxycyclopentene (3b):14,15,16b,18 IR (CH2Cl2, νmax, 1645 cm-1. 1H NMR (400 MHz, CDCl3, δ, 0.20 [s, 9 H, Si(CH3)3, 1.82-1.90 (m, 2 H, CH 2, 2.24-2.29 (m, 4 H, 2 x CH2, 4.62-4.63 (m, 1 H, CH, 6-Methyl-1-trimethylsilyloxy-1-cyclohexene (3c):14,15,17 IR (CH2Cl2, νmax, 1660 cm-1. 1H NMR (400 MHz, CDCl3, δ, 0.19 [s, 9 H, SiCH3
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2, J = 7.8 Hz), 5.32 (t, 1 H, CH, J = 4.6 Hz), 7.21-7.36 (m, 3 H, 3 x ArCH), 7.54 (d, 1 H, ArCH, J = 7.4 Hz).
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0001556758
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Bonafoux, D.; Bordeau, M.; Biran, C.; Cazeau, P.; Dunogues, J. J. Org. Chem. 1996, 61, 5532.
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45849146141
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Commercially available from Aldrich Chemical Co, CAS, 6651-36-1, cat. no. 144819
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(a) Commercially available from Aldrich Chemical Co., CAS# [6651-36-1], cat. no. 144819;
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36
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45849118308
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Commercially available from Aldrich Chemical Co., CAS# [19980-43-9], cat. no. 283126;
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(b) Commercially available from Aldrich Chemical Co., CAS# [19980-43-9], cat. no. 283126;
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37
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45849103109
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Commercially available from Aldrich Chemical Co, CAS, 38858-72-9, cat. no. 540390
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(c) Commercially available from Aldrich Chemical Co., CAS# [38858-72-9], cat. no. 540390.
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