(E)-pent-2-enal

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Sodium (4.02 g, 0.175 mol) was dissolved in a stirred solution of diethyl acetamidomalonate (235.4 g, 1.19 mol) in abs EtOH (1.4 L) at ambient temperature under argon. The reaction mixture was cooled to 0° C., and trans-2-pentenal (100 g, 1.08 mol) was added dropwise maintaining the reaction temperature at <5° C. After the addition, the reaction was allowed to warm to room temperature, stirred for 4 h, then quenched with acetic acid (28 mL). The solution was concentrated in vacuo, and the residue dissolved in EtOAc (1.5 L), washed with 10% NaHCO3 solution (2×300 mL), brine, and dried (MgSO4). The solution was filtered and concentrated to 700 mL, then heated to reflux and treated with hexane (1 L). On cooling, the title compound precipitated and was collected to give 287 g. 1H NMR (CD3OD) δ5.65 (d, 1H, J=5 Hz), 4.1-4.25 (m, 4H), 2.7-2.8 (m, 1H), 2.21 (s, 3H), 2.10 (dd, 1H, J=6, 13, Hz),1.86-1.97 (m, 2H), 1.27 (t, 3H, J=7 Hz), 1.23 (t, 3H, J=7 Hz), 1.1-1.25 (m, 1H), 0.97 (t, 3H, J=7 Hz). maintaining the reaction temperature at <5° C After the addition to warm to room temperature quenched with acetic acid (28 mL) The solution was concentrated in vacuo the residue dissolved in EtOAc (1.5 L) washed with 10% NaHCO3 solution (2×300 mL), brine dried (MgSO4) The solution was filtered concentrated to 700 mL heated to reflux treated with hexane (1 L) On cooling the title compound precipitated was collected to give 287 g

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Sodium (4.02 g, 0.175 mol) was dissolved in a stirred solution of diethyl acetamidomalonate (235.4 g, 1.19 mol) in abs EtOH (1.4 L) at ambient temperature under argon. The reaction mixture was cooled to 0° C., and trans-2-pentenal (100 g, 1.08 mol) was added dropwise maintaining the reaction temperature at <5° C. After the addition, the reaction was allowed to warm to room temperature, stirred for 4 h, then quenched with acetic acid (28 mL). The solution was concentrated in vacuo, and the residue dissolved in EtOAc (1.5 L), washed with 10% NaHCO3 solution (2×300 mL), brine, and dried (MgSO4). The solution was filtered and concentrated to 700 mL, then heated to reflux and treated with hexane (1 L). On cooling, the title compound precipitated and was collected, mp 106°-109° C. 1H NMR (CD3OD) δ 5.65 (d, 1H, J=5 Hz), 4.1-4.25 (m, 4H), 2.7-2.8 (m, 1H), 2.21 (s, 3H), 2.10 (dd, 1H, J=6, 13, Hz),1.86-1.97 (m, 2H), 1.27 (t, 3H, J=7 Hz), 1.23 (t, 3H, J=7 Hz), 1.1-1.25 (m, 1H), 0.97 (t, 3H, J=7 Hz). maintaining the reaction temperature at <5° C After the addition to warm to room temperature quenched with acetic acid (28 mL) The solution was concentrated in vacuo the residue dissolved in EtOAc (1.5 L) washed with 10% NaHCO3 solution (2×300 mL), brine dried (MgSO4) The solution was filtered concentrated to 700 mL heated to reflux treated with hexane (1 L) On cooling the title compound precipitated was collected

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

Procedure: A vial was charged with aminoalcohol A (0.0063 g, 0.026 mmol). To the vial was added 1.68 mL of a stock solution containing trans-2-pentenal (0.34 g), t-butylbenzene internal standard (0.25 g), 1 M diethylzinc in hexane (8.0 mL), and toluene (4.0 mL). After 48 h acetic anhydride (0.200 mL) was added. After an additional 72 h a sample of the solution was analyzed by gas chromatography at 80° C. on a Cyclodex B stationary phase. The product trans-4-hepten-3-yl acetate was formed 87% enantiomeric excess.

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

Procedure: A vial was charged with aminoalcohol A (0.0063 g, 0.026 mmol). To the vial was added 1.68 mL of a stock solution containing trans-2-pentenal (0.34 g), t-butylbenzene internal standard (0.25 g), 1 M diethylzinc in hexane (8.0 mL), and toluene (4.0 mL). After 48 h acetic anhydride (0.200 mL) was added. After an additional 72 h a sample of the solution was analyzed by gas chromatography at 80° C. on a Cyclodex B stationary phase. The product trans-4-hepten-3-yl acetate was formed 87% enantiomeric excess.

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

Procedure: A vial was charged with aminoalcohol 1 (0.0032 g, 0.011 mmol) prepared as in Example 1. To the vial was added 1.62 mL of a stock solution containing trans-2-pentenal (0.34 g), t-butylbenzene internal standard (0.25 g), 1 M diethylzinc in hexane (8.0 mL), and toluene (4.0 mL). After 48 h, acetic anhydride (0.200 mL) was added. After an additional 72 h, a sample of the solution was analyzed by gas chromatography at 80° C. on a Cyclodex B stationary phase. The product trans4hepten-3-yl acetate was formed 85% enantiomeric excess. After an additional 72 h was analyzed by gas chromatography at 80° C. on a Cyclodex B stationary phase

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

Procedure: A vial was charged with aminoalcohol 1 (0.0032 g, 0.011 mmol) prepared as in Example 1. To the vial was added 1.62 mL of a stock solution containing trans-2-pentenal (0.34 g), t-butylbenzene internal standard (0.25 g), 1 M diethylzinc in hexane (8.0 mL), and toluene (4.0 mL). After 48 h, acetic anhydride (0.200 mL) was added. After an additional 72 h, a sample of the solution was analyzed by gas chromatography at 80° C. on a Cyclodex B stationary phase. The product trans4hepten-3-yl acetate was formed 85% enantiomeric excess. After an additional 72 h was analyzed by gas chromatography at 80° C. on a Cyclodex B stationary phase

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: N,N-Dimethylhydrazine (42.0 mL 0.55 mol) was added dropwise to trans-2-pentenal (42.06 g, 0.50 mol) at such a rate that the reaction temperature could be maintained at about 0° C. The mixture was then stirred for 1 h at ambient temperature, and the organic phase separated and dried (K2CO3). Distillation (bp 84°-86° C., 25 mm Hg; lit bp 60° C., 15 mm Hg) through a 10 cm Vigreaux column gave trans-2-pentenal N,N-dimethylhydrazone (12) (51.3 g, 81%): n20 1.5104; IR (neat) 2960, 2870, 2850, 2820, 2780, 1565, 1470, 1460, 1445, 1265, 1135, 1030, 970 cm-1 ; 1H NMR (CDCl3) δ0.98 (t, 3 H, J=7.4 Hz), 2.16-2.05 (m, 2 H), 2.76 (s, 6 H), 5.82 (dt, 1 H, J= 15.6, 6.3 Hz), 6.14 (dd, 1 H, J=15.6, 8.8 Hz) 6.97 (d, 1 H, J=8.8 Hz). the organic phase separated dried (K2CO3) Distillation (bp 84°-86° C., 25 mm Hg; lit bp 60° C., 15 mm Hg) through a 10 cm Vigreaux column

Conditions: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: N,N-Dimethylhydrazine (42.0 mL 0.55 mol) was added dropwise to trans-2-pentenal (42.06 g, 0.50 mol) at such a rate that the reaction temperature could be maintained at about 0° C. The mixture was then stirred for 1 h at ambient temperature, and the organic phase separated and dried (K2CO3). Distillation (bp 84°-86° C., 25 mm Hg; lit bp 60° C., 15 mm Hg) through a 10 cm Vigreaux column gave trans-2-pentenal N,N-dimethylhydrazone (12) (51.3 g, 81%): n20 1.5104; IR (neat) 2960, 2870, 2850, 2820, 2780, 1565, 1470, 1460, 1445, 1265, 1135, 1030, 970 cm-1 ; 1H NMR (CDCl3) δ0.98 (t, 3 H, J=7.4 Hz), 2.16-2.05 (m, 2 H), 2.76 (s, 6 H), 5.82 (dt, 1 H, J= 15.6, 6.3 Hz), 6.14 (dd, 1 H, J=15.6, 8.8 Hz) 6.97 (d, 1 H, J=8.8 Hz). the organic phase separated dried (K2CO3) Distillation (bp 84°-86° C., 25 mm Hg; lit bp 60° C., 15 mm Hg) through a 10 cm Vigreaux column

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

Procedure: A vial was charged with aminoalcohol A (0.0063 g, 0.026 mmol). To the vial was added 1.68 mL of a stock solution containing trans-2-pentenal (0.34 g), t-butylbenzene internal standard (0.25 g), 1 M diethylzinc in hexane (8.0 mL), and toluene (4.0 mL). After 48 h acetic anhydride (0.200 mL) was added. After an additional 72 h a sample of the solution was analyzed by gas chromatography at 80° C. on a Cyclodex B stationary phase. The product trans-4-hepten-3-yl acetate was formed 87% enantiomeric excess.

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

Procedure: A vial was charged with aminoalcohol 1 (0.0032 g, 0.011 mmol) prepared as in Example 1. To the vial was added 1.62 mL of a stock solution containing trans-2-pentenal (0.34 g), t-butylbenzene internal standard (0.25 g), 1 M diethylzinc in hexane (8.0 mL), and toluene (4.0 mL). After 48 h, acetic anhydride (0.200 mL) was added. After an additional 72 h, a sample of the solution was analyzed by gas chromatography at 80° C. on a Cyclodex B stationary phase. The product trans4-hepten-3-yl acetate was formed 85% enantiomeric excess. After an additional 72 h was analyzed by gas chromatography at 80° C. on a Cyclodex B stationary phase

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

Procedure: A vial was charged with aminoalcohol 1 (0.0032 g, 0.011 mmol) prepared as in Example 1. To the vial was added 1.62 mL of a stock solution containing trans-2-pentenal (0.34 g), t-butylbenzene internal standard (0.25 g), 1 M diethylzinc in hexane (8.0 mL), and toluene (4.0 mL). After 48 h, acetic anhydride (0.200 mL) was added. After an additional 72 h, a sample of the solution was analyzed by gas chromatography at 80° C. on a Cyclodex B stationary phase. The product trans4-hepten-3-yl acetate was formed 85% enantiomeric excess. After an additional 72 h was analyzed by gas chromatography at 80° C. on a Cyclodex B stationary phase

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

Procedure: To a 500 mL round-bottom flask equipped with a stir bar was added (S)-2-(diphenyl((trimethylsilyl)oxy)methyl)pyrrolidine (2.60 g, 8.00 mmol) and CHCl3 (200 mL). To the solution was added tert-butyl tosylcarbamate (10.9 g, 40.0 mmol). The flask was placed in a room temperature-water bath. To the stirred solution was added sodium acetate (9.84 g, 120 mmol), then (E)-pent-2-enal (4.04 g, 48.0 mmol). The mixture was stirred at room temperature for 40 minutes. The mixture was filtered, washing the filter cake with a small amount of CHCl3. The filtrate was concentrated in vacuo at 30° C. The resulting orange liquid was dissolved in Et2O (400 mL) and transfered to a 1 L separatory funnel. The solution was washed with water:aq. sat. NaHCO3 (200 mL:200 mL). The aqueous phase was extracted with Et2O (100 mL). The combined organics were washed with brine (200 mL); dried over MgSO4; filtered; then concentrated in vacuo to afford (2R,3S)-tert-butyl 2-ethyl-3-formylaziridine-1-carboxylate as a pale orange liquid. To a 500 mL round-bottom flask equipped with a stir bar was placed in a room temperature The mixture was filtered washing the filter cake with a small amount of CHCl3 The filtrate was concentrated in vacuo at 30° C The resulting orange liquid was dissolved in Et2O (400 mL) transfered to a 1 L separatory funnel The solution was washed with water The aqueous phase was extracted with Et2O (100 mL) The combined organics were washed with brine (200 mL) dried over MgSO4 filtered then concentrated in vacuo