benzyl pent-4-enoate

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

Procedure: Benzyl bromide (7.19 g, 42.04 mmol) was added to a solution of 4-pentenoic acid (6) (5.05 g, 50.45 mmol, 1.2 eq.) in acetone (75 ml) at RT under N2. Anhydrous potassium carbonate (29.05 g, 210.19 mmol, 5.0 eq.) and tetrabutylammonium iodide (0.776 g, 2.102 mmol, 0.05 eq.) were added and the resulting suspension was stirred over 2 days. LCMS analysis showed mainly product.

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of crude 1-chlorosilolane (0.317 g) and benzyl pent-4-enoate (0.50 g; 2.63 mmol) under argon was added two drops of Karstedt's catalyst solution (in xylenes; ˜2% Pt). The reaction vessel was sealed and the mixture was heated to 60° C. for 18 hours. The crude liquid was used without purification. The reaction vessel was sealed The crude liquid was used without purification

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of crude 1-chlorosilolane (0.317 g) and benzyl pent-4-enoate (0.50 g; 2.63 mmol) under argon was added two drops of Karstedt's catalyst solution (in xylenes; ˜2% Pt). The reaction vessel was sealed and the mixture was heated to 60° C. for 18 hours. The crude liquid was used without purification. The reaction vessel was sealed The crude liquid was used without purification

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of crude 1-chlorosilinane (0.35 g) and benzyl pent-4-enoate (0.50 g; 2.63 mmol) under argon was added two drops of Karstedt's catalyst solution (in xylenes; ˜2% Pt). The reaction vessel was sealed and the mixture was heated to 60° C. for 16 hours. The crude liquid was used without purification. The reaction vessel was sealed The crude liquid was used without purification

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of chlorodiphenylsilane (0.49 g; 2.58 mmol) and benzyl pent-4-enoate (0.50 g; 2.58 mmol) under argon was added two drops of Karstedt's catalyst solution (in xylenes; ˜2% Pt). The reaction vessel was sealed and the mixture was heated to 60° C. for 15 hours. The crude liquid was used without purification. The reaction vessel was sealed The crude liquid was used without purification

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of chlorodiphenylsilane (0.49 g; 2.58 mmol) and benzyl pent-4-enoate (0.50 g; 2.58 mmol) under argon was added two drops of Karstedt's catalyst solution (in xylenes; ˜2% Pt). The reaction vessel was sealed and the mixture was heated to 60° C. for 15 hours. The crude liquid was used without purification. The reaction vessel was sealed The crude liquid was used without purification

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of chlorodimethylsilane (0.730 g; 6.57 mmol) and benzyl pent-4-enoate (1.25 g; 6.57 mmol) under argon was added one drop of Karstedt's catalyst solution (in xylenes; ˜2% Pt). The reaction vessel was sealed and the mixture was heated to 60° C. for 13.5 hours. The crude liquid was used without purification. The reaction vessel was sealed The crude liquid was used without purification

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

Procedure: N-Methyl-N-nitrosourea (6.4 g, 31 mmol) was added to an ice-cooled mixture of 10% aqueous NaOH (250 g, 625 mmol) and Et2O (300 mL), and the mixture was stirred vigorously with ice cooling for 10 minutes. The ether layer was decanted into a dry, 1 L Erlenmeyer flask, and stirred with ice cooling as a solution of the product from Example 114A (3.00 g, 15.8 mmol) in ether (60 mL) was added. The yellow solution was stirred with ice cooling as Pd(OAc)2 (30 mg, 0.134 mmol) was added. After 1 hour, acetic acid (0.5 mL) was added to consume any excess diazomethane, and the reaction mixture was concentrated under vacuum to a gray oil. The residue was dissolved in EtOAc (50 mL) and washed with saturated NaHCO3(aq) (25 mL). The organic phase was concentrated under vacuum and the residue was purified by flash chromatography (silica gel, eluted with hexanes-EtOAc 100:0-90:10) to provide the title compound. 1H NMR (300 MHz, CD3OD) δ ppm −0.02-0.06 (m, 2H) 0.40 (ddd, J=8.1, 5.8, 4.1 Hz, 2H) 0.62-0.78 (m, 1H) 1.51 (q, J=7.1 Hz, 2H) 2.45 (t, J=7.3 Hz, 2H) 5.11 (s, 2H) 7.24-7.40 (m, 5H). cooled The ether layer was decanted into a dry, 1 L Erlenmeyer flask was added was added After 1 hour to consume any excess diazomethane the reaction mixture was concentrated under vacuum to a gray oil The residue was dissolved in EtOAc (50 mL) washed with saturated NaHCO3(aq) (25 mL) The organic phase was concentrated under vacuum the residue was purified by flash chromatography (silica gel, eluted with hexanes-EtOAc 100:0-90:10)

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

Procedure: A suspension of K2CO3 (4.17 g, 30.2 mmol) and pent-4-enoic acid (3.01 g, 29.2 mmol) in DMF (25 mL) was stirred at room temperature for 5 minutes. Benzyl bromide (3.55 mL, 29.3 mmol) was added from a syringe over 3 minutes, and the resulting white suspension was stirred at room temperature for 23 hours, then diluted with water (150 mL) and extracted with EtOAc (3×50 mL). The combined extract was washed with saturated brine (30 mL) and concentrated under vacuum to leave the title compound. 1H NMR (300 MHz, CD3OD) δ ppm 2.30-2.41 (m, 2H) 2.42-2.50 (m, 2H) 4.96 (dddd, J=10.2, 1.7, 1.4, 1.0 Hz, 1H) 5.03 (dq, J=17.3, 1.6 Hz, 1H) 5.11 (s, 2H) 5.82 (tdd, J=17.0, 10.4, 6.3 Hz, 1H) 7.25-7.38 (m, 5H). the resulting white suspension was stirred at room temperature for 23 hours extracted with EtOAc (3×50 mL) The combined extract was washed with saturated brine (30 mL) concentrated under vacuum

Conditions: temp:40.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 10.53 g (105 mmol) of pent-4-enoic acid in 150 ml ethanol was added 17.1 g (52.5 mmol) of Cs2CO3 and the reaction mixture was stirred at 40° C. for 2 h. The solvent was removed in vacuo, the residue coevaporated three times with toluene and then dissolved in 150 ml of DMF. 17.96 g (105 mmol) of benzyl bromide were added and the reaction mixture stirred at room temperature for 48 h. The reaction mixture was filtered, diluted with water and extracted three times with heptane. The combined organic phases were dried over MgSO4, filtered and the solvent was removed in vacuo. Yield: 19.92 g. The solvent was removed in vacuo dissolved in 150 ml of DMF the reaction mixture stirred at room temperature for 48 h The reaction mixture was filtered diluted with water extracted three times with heptane The combined organic phases were dried over MgSO4 filtered the solvent was removed in vacuo

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

Procedure: Benzyl bromide (7.19 g, 42.04 mmol) was added to a solution of 4-pentenoic acid (6) (5.05 g, 50.45 mmol, 1.2 eq.) in acetone (75 ml) at RT under N2. Anhydrous potassium carbonate (29.05 g, 210.19 mmol, 5.0 eq.) and tetrabutylammonium iodide (0.776 g, 2.102 mmol, 0.05 eq.) were added and the resulting suspension was stirred over 2 days. LCMS analysis showed mainly product.

Conditions: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of crude 1-chlorosilolane (0.317 g) and benzyl pent-4-enoate (0.50 g; 2.63 mmol) under argon was added two drops of Karstedt's catalyst solution (in xylenes; ˜2% Pt). The reaction vessel was sealed and the mixture was heated to 60° C. for 18 hours. The crude liquid was used without purification. The reaction vessel was sealed The crude liquid was used without purification