3-methyl-1-(3-methylbutylsulfanyl)butane

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Borane-diisoamyl sulfide (5.0 ml, 21 mmol) was dissolved in THF (20 ml) and (-)-β-pinene (8.86 g, 64 mmol), [α]23D=-20.8° (neat), 91% ee, was added at 0° C. The mixture was kept at room temperature for 1 h and oxidized by the addition of 3M sodium hydroxide (10 ml, 30 mmol) and 30% hydrogen peroxide (7 ml, 70 mmol) keeping the temperature during the addition below 30° C. and then stirring at room temperature for 3 h. The mixture was saturated with potassium carbonate, the THF layer was separated and the aqueous layer was extracted with diethyl ether (2×50 ml). The extracts were combined with the THF solution, dried over magnesium sulfate and distilled using a Widmer column to give a first fraction, 4.25 g, bp 45°-58° C./0.1 mm Hg composed of diisoamyl sulfide (77%) and cis-myrtanol (23%) and a second fraction 7.96 g (82%), bp 58°-60° C./0.1 mm Hg, n20D=1.4907, [α]°D=-19.4° (neat). during the addition below 30° C. the THF layer was separated the aqueous layer was extracted with diethyl ether (2×50 ml) dried over magnesium sulfate distilled to give a first fraction, 4.25 g, bp 45°-58° C./0.1 mm Hg n20D=1.4907, [α]°D=-19.4° (neat)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Borane-diisoamyl sulfide (5.0 ml, 21 mmol) was dissolved in THF (20 ml) and (-)-β-pinene (8.86 g, 64 mmol), [α]23D=-20.8° (neat), 91% ee, was added at 0° C. The mixture was kept at room temperature for 1 h and oxidized by the addition of 3M sodium hydroxide (10 ml, 30 mmol) and 30% hydrogen peroxide (7 ml, 70 mmol) keeping the temperature during the addition below 30° C. and then stirring at room temperature for 3 h. The mixture was saturated with potassium carbonate, the THF layer was separated and the aqueous layer was extracted with diethyl ether (2×50 ml). The extracts were combined with the THF solution, dried over magnesium sulfate and distilled using a Widmer column to give a first fraction, 4.25 g, bp 45°-58° C./0.1 mm Hg composed of diisoamyl sulfide (77%) and cis-myrtanol (23%) and a second fraction 7.96 g (82%), bp 58°-60° C./0.1 mm Hg, n20D=1.4907, [α]°D=-19.4° (neat). during the addition below 30° C. the THF layer was separated the aqueous layer was extracted with diethyl ether (2×50 ml) dried over magnesium sulfate distilled to give a first fraction, 4.25 g, bp 45°-58° C./0.1 mm Hg n20D=1.4907, [α]°D=-19.4° (neat)

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Diborane generated as described in Example 6 was passed through a bubbler containing sodium borohydride (0.1 g) in diglyme (5 ml) and a trap cooled to -78° C. was absorbed in neat diisoamyl sulfide (8.67 g, 50 mmol) at 0° C. Excess diborane was absorbed in the next bubbler containing tetrahydrofuran (10 ml) over mercury and cooled in ice water. A mercury bubbler was connected to the exit. Diborane was passed into the sulfide until the concentration of borane in THF reached 1M. Borane-diisoamyl sulfide, a colorless liquid, was stirred overnight at room temperature prior to disconnecting the bubblers and then analyzed for active hydride by a standard procedure using a water-glycerol-methanol 1:1:1 hydrolyzing mixture. Concentration 4.2M, 11B NMR, δ, -22.5 ppm. Excess diborane was absorbed in the next bubbler containing tetrahydrofuran (10 ml) over mercury cooled in ice water

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Isoamyl bromide (21.88 g, 0.21 mol) and tetrabutylammonium bromide (1.61 g, 5 mmol) were added to a solution of sodium sulfide nonahydrate (24.02 g, 0.10 mol) in water (50 ml) and the mixture was refluxed with stirring for 6 h. The organic layer was separated, the aqueous layer was extracted with pentane (25 ml). The extract was combined with the organic layer and dried with anhydrous magnesium sulfate. Distillation gave 15.85 g, 91% of a colorless liquid, bp 49°-50° C./0.1 mm Hg, n20D=1.4514, >99% GC pure; 1H NMR (CDCl3) δ 0.95 (d, J=6 Hz, 12H, CH3), 1.47 (q, J=6 Hz, 4H, CH2), 1.68 (septet, J=6 Hz, 2H, CH), 2.51 (t, J=6 Hz, 4H, CH2). the mixture was refluxed The organic layer was separated the aqueous layer was extracted with pentane (25 ml) dried with anhydrous magnesium sulfate Distillation

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Isoamyl bromide (21.88 g, 0.21 mol) and tetrabutylammonium bromide (1.61 g, 5 mmol) were added to a solution of sodium sulfide nonahydrate (24.02 g, 0.10 mol) in water (50 ml) and the mixture was refluxed with stirring for 6 h. The organic layer was separated, the aqueous layer was extracted with pentane (25 ml). The extract was combined with the organic layer and dried with anhydrous magnesium sulfate. Distillation gave 15.85 g, 91% of a colorless liquid, bp 49°-50° C./0.1 mm Hg, n20D=1.4514, >99% GC pure; 1H NMR (CDCl3) δ 0.95 (d, J=6 Hz, 12H, CH3), 1.47 (q, J=6 Hz, 4H, CH2), 1.68 (septet, J=6 Hz, 2H, CH), 2.51 (t, J=6 Hz, 4H, CH2). the mixture was refluxed The organic layer was separated the aqueous layer was extracted with pentane (25 ml) dried with anhydrous magnesium sulfate Distillation

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Borane-diisoamyl sulfide (5.0 ml, 21 mmol) was dissolved in THF (20 ml) and (-)-β-pinene (8.86 g, 64 mmol), [α]23D=-20.8° (neat), 91% ee, was added at 0° C. The mixture was kept at room temperature for 1 h and oxidized by the addition of 3M sodium hydroxide (10 ml, 30 mmol) and 30% hydrogen peroxide (7 ml, 70 mmol) keeping the temperature during the addition below 30° C. and then stirring at room temperature for 3 h. The mixture was saturated with potassium carbonate, the THF layer was separated and the aqueous layer was extracted with diethyl ether (2×50 ml). The extracts were combined with the THF solution, dried over magnesium sulfate and distilled using a Widmer column to give a first fraction, 4.25 g, bp 45°-58° C./0.1 mm Hg composed of diisoamyl sulfide (77%) and cis-myrtanol (23%) and a second fraction 7.96 g (82%), bp 58°-60° C./0.1 mm Hg, n20D=1.4907, [α]°D=-19.4° (neat). during the addition below 30° C. the THF layer was separated the aqueous layer was extracted with diethyl ether (2×50 ml) dried over magnesium sulfate distilled to give a first fraction, 4.25 g, bp 45°-58° C./0.1 mm Hg n20D=1.4907, [α]°D=-19.4° (neat)

反応条件: temp:-78.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Diborane generated as described in Example 6 was passed through a bubbler containing sodium borohydride (0.1 g) in diglyme (5 ml) and a trap cooled to -78° C. was absorbed in neat diisoamyl sulfide (8.67 g, 50 mmol) at 0° C. Excess diborane was absorbed in the next bubbler containing tetrahydrofuran (10 ml) over mercury and cooled in ice water. A mercury bubbler was connected to the exit. Diborane was passed into the sulfide until the concentration of borane in THF reached 1M. Borane-diisoamyl sulfide, a colorless liquid, was stirred overnight at room temperature prior to disconnecting the bubblers and then analyzed for active hydride by a standard procedure using a water-glycerol-methanol 1:1:1 hydrolyzing mixture. Concentration 4.2M, 11B NMR, δ, -22.5 ppm. Excess diborane was absorbed in the next bubbler containing tetrahydrofuran (10 ml) over mercury cooled in ice water

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Isoamyl bromide (21.88 g, 0.21 mol) and tetrabutylammonium bromide (1.61 g, 5 mmol) were added to a solution of sodium sulfide nonahydrate (24.02 g, 0.10 mol) in water (50 ml) and the mixture was refluxed with stirring for 6 h. The organic layer was separated, the aqueous layer was extracted with pentane (25 ml). The extract was combined with the organic layer and dried with anhydrous magnesium sulfate. Distillation gave 15.85 g, 91% of a colorless liquid, bp 49°-50° C./0.1 mm Hg, n20D=1.4514, >99% GC pure; 1H NMR (CDCl3) δ 0.95 (d, J=6 Hz, 12H, CH3), 1.47 (q, J=6 Hz, 4H, CH2), 1.68 (septet, J=6 Hz, 2H, CH), 2.51 (t, J=6 Hz, 4H, CH2). the mixture was refluxed The organic layer was separated the aqueous layer was extracted with pentane (25 ml) dried with anhydrous magnesium sulfate Distillation