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Volumn , Issue 9, 2008, Pages 1386-1390

Di-tert-butylmagnesium as an atom-efficient, carbon-centred base reagent for the preparation of silyl enol ethers from ketones

Author keywords

Deprotonations; Grignard reagents; Ketones; Magnesium; Organometallic reagents

Indexed keywords

CARBON; ETHER DERIVATIVE; GRIGNARD REAGENT; KETONE DERIVATIVE; MAGNESIUM DERIVATIVE;

EID: 45849144762     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2008-1072739     Document Type: Article
Times cited : (7)

References (47)
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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.
    • (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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    • For both the efficacy and issues with reagents such as the commonly used lithium-based amides, see: a, Paquette, L. A, Ed, Wiley: Chichester
    • 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.
    • (1995) Encyclopedia of Reagents for Organic Synthesis , vol.5 , pp. 3096
    • Bakker, W.I.I.1    Wong, P.L.2    Snieckus, V.3
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    • Scheffold, R, Ed, Wiley-VCH: New York
    • (b) Heathcock, C. H. In Modern Synthetic Methods, Vol. 3; Scheffold, R., Ed.; Wiley-VCH: New York, 1992, 3.
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    • Trost, B. M, Fleming, I, Eds, Pergamon: Oxford
    • (c) Caine, D. In Comprehensive Organic Synthesis, Vol. 3; Trost, B. M.; Fleming, I., Eds.; Pergamon: Oxford, 1991, 1.
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    • Caine, D.1
  • 14
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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.
    • 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.
  • 16
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    • For the use of base reagent mixtures with n-BuLi, see ref. 2e and 2f.
    • (c) For the use of base reagent mixtures with n-BuLi, see ref. 2e and 2f.
  • 17
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    • 1.5 mol of the complex (i.e., 4.5 equiv of base) was required at 125°C
    • 3 to perform effectively in deprotonation reactions
    • 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.
  • 29
    • 45849116887 scopus 로고    scopus 로고
    • 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
    • -1; (iv) final oven temperature, 190°C; and (v) detection method, FID.
  • 30
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    • For the preparation of dialkylmagnesium reagents using 1,4-dioxane, see:, Academic Press: London
    • For the preparation of dialkylmagnesium reagents using 1,4-dioxane, see: Wakefield, B. J. Organomagnesium Methods in Organic Synthesis; Academic Press: London, 1995.
    • (1995) Organomagnesium Methods in Organic Synthesis
    • Wakefield, B.J.1
  • 31
    • 45849120959 scopus 로고    scopus 로고
    • 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
    • 13
  • 32
    • 45849148057 scopus 로고    scopus 로고
    • 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
    • 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).
  • 35
    • 45849146141 scopus 로고    scopus 로고
    • Commercially available from Aldrich Chemical Co, CAS, 6651-36-1, cat. no. 144819
    • (a) Commercially available from Aldrich Chemical Co., CAS# [6651-36-1], cat. no. 144819;
  • 36
    • 45849118308 scopus 로고    scopus 로고
    • Commercially available from Aldrich Chemical Co., CAS# [19980-43-9], cat. no. 283126;
    • (b) Commercially available from Aldrich Chemical Co., CAS# [19980-43-9], cat. no. 283126;
  • 37
    • 45849103109 scopus 로고    scopus 로고
    • Commercially available from Aldrich Chemical Co, CAS, 38858-72-9, cat. no. 540390
    • (c) Commercially available from Aldrich Chemical Co., CAS# [38858-72-9], cat. no. 540390.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.