cycloocten-1-yloxy(trimethyl)silane

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 42 g (0.38 mol) of chlorotrimethylsilane and 78 g of triethylamine in 100 ml of dimethylformamide, a solution of 32 g (0.254 mol) of cyclooctanone in 40 ml of dimethylformamide was added. The resultant mixture was stirred at 100° to 115° C. for 48 hours. At the end of the reaction, the reaction mixture was combined with 240 ml of n-hexane and washed twice with 300 ml of a saturated aqueous sodium bicarbonate solution. The mixture was washed under cooling with 180 ml of 1.5N hydrochloric acid, then washed sequentially with an aqueous sodium bicarbonate solution, water, and saline and then dried with magnesium sulfate. The mixture was concentrated and distilled under vacuum, to afford 40 g (80% yield) of 1-cyclooctenyloxytrimethylsilane having a boiling point of 82° to 84° C./5 mmHg. At the end of the reaction washed twice with 300 ml of a saturated aqueous sodium bicarbonate solution The mixture was washed under cooling with 180 ml of 1.5N hydrochloric acid washed sequentially with an aqueous sodium bicarbonate solution, water, and saline dried with magnesium sulfate The mixture was concentrated distilled under vacuum

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 42 g (0.38 mol) of chlorotrimethylsilane and 78 g of triethylamine in 100 ml of dimethylformamide, a solution of 32 g (0.254 mol) of cyclooctanone in 40 ml of dimethylformamide was added. The resultant mixture was stirred at 100° to 115° C. for 48 hours. At the end of the reaction, the reaction mixture was combined with 240 ml of n-hexane and washed twice with 300 ml of a saturated aqueous sodium bicarbonate solution. The mixture was washed under cooling with 180 ml of 1.5N hydrochloric acid, then washed sequentially with an aqueous sodium bicarbonate solution, water, and saline and then dried with magnesium sulfate. The mixture was concentrated and distilled under a vacuum, to afford 40 g (80% in yield) of 1-cyclooctenyloxytrimethylsilane having a boiling point of 82° to 84° C./5 mmHg. At the end of the reaction washed twice with 300 ml of a saturated aqueous sodium bicarbonate solution The mixture was washed under cooling with 180 ml of 1.5N hydrochloric acid washed sequentially with an aqueous sodium bicarbonate solution, water, and saline dried with magnesium sulfate The mixture was concentrated distilled under a vacuum

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of 42 g (0.38 mol) of chlorotrimethylsilane and 78 g of triethylamine in 100 ml of dimethylformamide, a solution of 32 g (0.254 mol) of cyclooctanone in 40 ml of dimethylformamide was added. The resultant mixture was stirred at 100° to 115° C. for 48 hours. At the end of the reaction, the reaction mixture was combined with 240 ml of n-hexane and washed twice with 300 ml of a saturated aqueous sodium bicarbonate solution. The mixture was washed under cooling with 180 ml of 1.5N hydrochloric acid, then washed sequentially with an aqueous sodium bicarbonate solution, water, and saline and then dried with magnesium sulfate. The mixture was concentrated and distilled under vacuum, to afford 40 g (80% yield) of 1-cyclooctenyloxytrimethylsilane having a boiling point of 82° to 84° C./5 mmHg. At the end of the reaction washed twice with 300 ml of a saturated aqueous sodium bicarbonate solution The mixture was washed under cooling with 180 ml of 1.5N hydrochloric acid washed sequentially with an aqueous sodium bicarbonate solution, water, and saline dried with magnesium sulfate The mixture was concentrated distilled under vacuum

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of silyl enol ether 6 (57.8 g, 291 mmol) in DMF (350 mL) was added a solution of Selectfluor (124 g, 349 mmol) in DMF (150 mL) over 1 h at rt. The solution was allowed to stir for 12 h. The reaction was quenched with 30 mL of H2O, and the DMF was removed on a rotary evaporator. The residue was diluted with hexanes (500 mL), washed with H2O (3×200 mL) and brine (1×50 mL), and dried over MgSO4. Following column chromatography (30:1 to 15:1 pentane/ether), a white solid was isolated (38.4 g, 91%, Rf=0.30 in 9:1 pentane/ether), mp 48.1-49.8° C. IR: 3429, 2932, 2859, 1721, 1709 cm1. (Lit: 1710 cm−1) (Rozen and Menahem. J. Fluorine Chem. (1980), 16, 19-31). 1H NMR (CDCl3, 400 MHz): δ 1.25 (m, 1H), 1.38-1.55 (m, 4H), 1.61 (m, 1H), 1.73 (m, 1H), 2.05 (m, 3H), 2.30 (m, 1H), 2.55 (m, 1H), 4.86 (ddd, 1H, J=49.6, 6.4, 2.8 Hz). (Lit: 1H NMR (CDCl3, 250 MHz): δ 1.36-2.7 (m, 12H), 4.9 (dm, 1H, J=49.5 Hz) (Chambers and Hutchinson J. Fluorine Chem. (1998) 89, 229-232) 13C NMR (CDCl3, 100 MHz): δ 20.3 (d, J=4.0 Hz), 24.4 (d, J=6.0 Hz), 24.5, 26.9, 32.2 (d, J=11.0 Hz), 39.3, 94.7 (d, J=185.0 Hz), 213.4 (d, J=21.0 Hz). (Lit: 13C NMR (CDCl3, 50 MHz): 620.5 (d, J=3.6 Hz), 24.6 (d, J=3.7 Hz), 24.7, 27.2, 32.7 (d, J=21.0 Hz), 39.6, 91.5 (d, J=184.7 Hz), 213.9 (d, J=20.9 Hz) (Chambers and Hutchinson (1998) supra) 19F NMR (CDCl3, 376 MHz): δ −190.7 (m). (Lit: 19F NMR (CDCl3, 235 MHz): δ −191.6 (m) (Chambers and Hutchinson (1998) supra) The reaction was quenched with 30 mL of H2O the DMF was removed on a rotary evaporator The residue was diluted with hexanes (500 mL) washed with H2O (3×200 mL) and brine (1×50 mL) dried over MgSO4 a white solid was isolated (38.4 g, 91%, Rf=0.30 in 9:1 pentane/ether), mp 48.1-49.8° C

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of cyclooctanone (40.0 g, 316 mmol) in 200 mL of anhydrous DMF were added triethylamine (TEA, 93.0 mL, 666 mmol) and chlorotrimethylsilane (84.0 mL, 666 mmol). The reaction was heated to reflux. After 15 h, the reaction was quenched with 20 mL of H2O and the DMF was removed on a rotary evaporator. The residue was diluted with hexanes (300 mL), washed with H2O (3×100 mL) and brine (1×50 mL), and dried over MgSO4. Distillation under reduced pressure (20 torr) yielded 58.1 g (93%) of the desired product as a colorless oil, bp 108° C. (20 torr) (lit. 106° C. at 25 torr). Nakamura, et al. J. Am. Chem. Soc. (1976) 98, 2346-2348. IR: 2926, 2851, 1661 cm−1. 1H NMR (CDCl3, 300 MHz): δ 0.20 (s, 9H), 1.39-1.58 (m, 8H), 2.02 (m, 2H), 2.19 (m, 2H), 4.75 (t, 1H, J=9.0 Hz). (Lit: 1H NMR (CDCl3, 600 MHz): δ 0.16 (s, 9H), 1.46 (m, 4H), 1.49 (m, 2H), 1.55 (m, 2H), 1.97 (m, 2H), 2.14 (m, 2H), 4.70 (t, 1H, J=8.0 Hz) (Frimer et al. J. Org. Chem. (2000) 65, 1807-1817.) 13C NMR (CDCl3, 75 MHz): δ 0.4, 25.5, 26.3, 26.4, 27.8, 30.9, 31.0, 105.41, 152.99. (Lit: 13C NMR (CDCl3, 150 MHz): δ 0.45, 25.52, 26.36, 26.40, 27.83, 30.98, 31.05, 105.45, 153.05) Frimer et al. (2000) supra) FAB-HRMS: Calcd. for C11H23OSi+ [M+H]+: 199.1518. found 199.1520. The reaction was heated to reflux the reaction was quenched with 20 mL of H2O the DMF was removed on a rotary evaporator The residue was diluted with hexanes (300 mL) washed with H2O (3×100 mL) and brine (1×50 mL) dried over MgSO4 Distillation under reduced pressure (20 torr)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of silyl enol ether 6 (57.8 g, 291 mmol) in DMF (350 mL) was added a solution of Selectfluor (124 g, 349 mmol) in DMF (150 mL) over 1 h at rt. The solution was allowed to stir for 12 h. The reaction was quenched with 30 mL of H2O, and the DMF was removed on a rotary evaporator. The residue was diluted with hexanes (500 mL), washed with H2O (3×200 mL) and brine (1×50 mL), and dried over MgSO4. Following column chromatography (30:1 to 15:1 pentane/ether), a white solid was isolated (38.4 g, 91%, Rf=0.30 in 9:1 pentane/ether), mp 48.1-49.8° C. IR: 3429, 2932, 2859, 1721, 1709 cm−1. (Lit: 1710 cm−1) (Rozen and Menahem. J. Fluorine Chem. (1980), 16, 19-31). 1H NMR (CDCl3, 400 MHz): δ 1.25 (m, 1H), 1.38-1.55 (m, 4H), 1.61 (m, 1H), 1.73 (m, 1H), 2.05 (m, 3H), 2.30 (m, 1H), 2.55 (m, 1H), 4.86 (ddd, 1H, J=49.6, 6.4, 2.8 Hz). (Lit: 1H NMR (CDCl3, 250 MHz): δ 1.36-2.7 (m, 12H), 4.9 (dm, 1H, J=49.5 Hz) (Chambers and Hutchinson J. Fluorine Chem. (1998) 89, 229-232)13C NMR (CDCl3, 100 MHz): δ 20.3 (d, J=4.0 Hz), 24.4 (d, J=6.0 Hz), 24.5, 26.9, 32.2 (d, J=11.0 Hz), 39.3, 94.7 (d, J=185.0 Hz), 213.4 (d, J=21.0 Hz). (Lit: 13C NMR (CDCl3, 50 MHz): δ 20.5 (d, J=3.6 Hz), 24.6 (d, J=3.7 Hz), 24.7, 27.2, 32.7 (d, J=21.0 Hz), 39.6, 91.5 (d, J=184.7 Hz), 213.9 (d, J=20.9 Hz) (Chambers and Hutchinson (1998) supra) 19F NMR (CDCl3, 376 MHz): δ −190.7 (m). (Lit: 19F NMR (CDCl3, 235 MHz): δ −191.6 (m) (Chambers and Hutchinson (1998) supra) The reaction was quenched with 30 mL of H2O the DMF was removed on a rotary evaporator The residue was diluted with hexanes (500 mL) washed with H2O (3×200 mL) and brine (1×50 mL) dried over MgSO4 a white solid was isolated (38.4 g, 91%, Rf=0.30 in 9:1 pentane/ether), mp 48.1-49.8° C

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of cyclooctanone (40.0 g, 316 mmol) in 200 mL of anhydrous DMF were added triethylamine (TEA, 93.0 mL, 666 mmol) and chlorotrimethylsilane (84.0 mL, 666 mmol). The reaction was heated to reflux. After 15 h, the reaction was quenched with 20 mL of H2O and the DMF was removed on a rotary evaporator. The residue was diluted with hexanes (300 mL), washed with H2O (3×100 mL) and brine (1×50 mL), and dried over MgSO4. Distillation under reduced pressure (20 torr) yielded 58.1 g (93%) of the desired product as a colorless oil, by 108° C. (20 torr) (lit. 106° C. at 25 torr). Nakamura, et al. J. Am. Chem. Soc. (1976) 98, 2346-2348. IR: 2926, 2851, 1661 cm−1. 1H NMR (CDCl3, 300 MHz): δ 0.20 (s, 9H), 1.39-1.58 (m, 8H), 2.02 (m, 2H), 2.19 (m, 2H), 4.75 (t, 1H, J=9.0 Hz). (Lit: 1H NMR (CDCl3, 600 MHz): δ 0.16 (s, 9H), 1.46 (m, 4H), 1.49 (m, 2H), 1.55 (m, 2H), 1.97 (m, 2H), 2.14 (m, 2H), 4.70 (t, 1H, J=8.0 Hz) (Frimer et al. J. Org. Chem. (2000) 65, 1807-1817.) 13C NMR (CDCl3, 75 MHz): δ 0.4, 25.5, 26.3, 26.4, 27.8, 30.9, 31.0, 105.41, 152.99. (Lit: 13C NMR (CDCl3, 150 MHz): δ 0.45, 25.52, 26.36, 26.40, 27.83, 30.98, 31.05, 105.45, 153.05) Frimer et al. (2000) supra) FAB-HRMS: Calcd. for C11H23OSi+ [M+H]+: 199.1518. found 199.1520. The reaction was heated to reflux the reaction was quenched with 20 mL of H2O the DMF was removed on a rotary evaporator The residue was diluted with hexanes (300 mL) washed with H2O (3×100 mL) and brine (1×50 mL) dried over MgSO4 Distillation under reduced pressure (20 torr)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of silyl enol ether 6 (57.8 g, 291 mmol) in DMF (350 mL) was added a solution of Selectfluor (124 g, 349 mmol) in DMF (150 mL) over 1 h at rt. The solution was allowed to stir for 12 h. The reaction was quenched with 30 mL of H2O, and the DMF was removed on a rotary evaporator. The residue was diluted with hexanes (500 mL), washed with H2O (3×200 mL) and brine (1×50 mL), and dried over MgSO4. Following column chromatography (30:1 to 15:1 pentane/ether), a white solid was isolated (38.4 g, 91%, Rf=0.30 in 9:1 pentane/ether), mp 48.1-49.8° C. IR: 3429, 2932, 2859, 1721, 1709 cm−1. (Lit: 1710 cm−1) (Rozen and Menahem. J. Fluorine Chem. (1980), 16, 19-31). 1H NMR (CDCl3, 400 MHz): δ 1.25 (m, 1H), 1.38-1.55 (m, 4H), 1.61 (m, 1H), 1.73 (m, 1H), 2.05 (m, 3H), 2.30 (m, 1H), 2.55 (m, 1H), 4.86 (ddd, 1H, J=49.6, 6.4, 2.8 Hz). (Lit: 1H NMR (CDCl3, 250 MHz): δ 1.36-2.7 (m, 12H), 4.9 (dm, 1H, J=49.5 Hz) (Chambers and Hutchinson J. Fluorine Chem. (1998) 89, 229-232) 13C NMR (CDCl3, 100 MHz): δ 20.3 (d, J=4.0 Hz), 24.4 (d, J=6.0 Hz), 24.5, 26.9, 32.2 (d, J=11.0 Hz), 39.3, 94.7 (d, J=185.0 Hz), 213.4 (d, J=21.0 Hz). (Lit: 13C NMR (CDCl3, 50 MHz): δ 20.5 (d, J=3.6 Hz), 24.6 (d, J=3.7 Hz), 24.7, 27.2, 32.7 (d, J=21.0 Hz), 39.6, 91.5 (d, J=184.7 Hz), 213.9 (d, J=20.9 Hz) (Chambers and Hutchinson (1998) supra) 19F NMR (CDCl3, 376 MHz): δ −190.7 (m). (Lit: 19F NMR (CDCl3, 235 MHz): δ −191.6 (m) (Chambers and Hutchinson (1998) supra) The reaction was quenched with 30 mL of H2O the DMF was removed on a rotary evaporator The residue was diluted with hexanes (500 mL) washed with H2O (3×200 mL) and brine (1×50 mL) dried over MgSO4 a white solid was isolated (38.4 g, 91%, Rf=0.30 in 9:1 pentane/ether), mp 48.1-49.8° C

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of cyclooctanone (40.0 g, 316 mmol) in 200 mL of anhydrous DMF were added triethylamine (TEA, 93.0 mL, 666 mmol) and chlorotrimethylsilane (84.0 mL, 666 mmol). The reaction was heated to reflux. After 15 h, the reaction was quenched with 20 mL of H2O and the DMF was removed on a rotary evaporator. The residue was diluted with hexanes (300 mL), washed with H2O (3×100 mL) and brine (1×50 mL), and dried over MgSO4. Distillation under reduced pressure (20 torr) yielded 58.1 g (93%) of the desired product as a colorless oil, by 108° C. (20 torr) (lit. 106° C. at 25 torr). Nakamura, et al. J. Am. Chem. Soc. (1976) 98, 2346-2348. IR: 2926, 2851, 1661 cm−1. 1H NMR (CDCl3, 300 MHz): δ 0.20 (s, 9H), 1.39-1.58 (m, 8H), 2.02 (m, 2H), 2.19 (m, 2H), 4.75 (t, 1H, J=9.0 Hz). (Lit: 1H NMR (CDCl3, 600 MHz): δ 0.16 (s, 9H), 1.46 (m, 4H), 1.49 (m, 2H), 1.55 (m, 2H), 1.97 (m, 2H), 2.14 (m, 2H), 4.70 (t, 1H, J=8.0 Hz) (Frimer et al. J. Org. Chem. (2000) 65, 1807-1817.) 13C NMR (CDCl3, 75 MHz): δ 0.4, 25.5, 26.3, 26.4, 27.8, 30.9, 31.0, 105.41, 152.99. (Lit: 13C NMR (CDCl3, 150 MHz): δ 0.45, 25.52, 26.36, 26.40, 27.83, 30.98, 31.05, 105.45, 153.05) Frimer et al. (2000) supra) FAB-HRMS: Calcd. for C11H23OSi+ [M+H]+: 199.1518, found 199.1520. The reaction was heated to reflux the reaction was quenched with 20 mL of H2O the DMF was removed on a rotary evaporator The residue was diluted with hexanes (300 mL) washed with H2O (3×100 mL) and brine (1×50 mL) dried over MgSO4 Distillation under reduced pressure (20 torr)