methyl 6-amino-6-sulfanylidenehexanoate

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

Procedure: Add THF (50 mL, anhydrous) to a roundbottom flask containing 5-thiocarbamoyl-pentanoic acid methyl ester (2.63 g, 15.0 mmol) and 2-bromo-1-(2-hydroxy-4-methoxy-phenyl)-ethanone (4.90 g, 15.0 mmol, 75% pure). Heat to reflux under N2 overnight. Cool to room temperature, add EtOAc, wash with saturated NaHCO3 solution, brine, and backextract from each aqueous layer with EtOAc. Dry combined organic layers over MgSO4 and concentrate to get 8 grams of a yellow solid. Adsorb on SiO2 and purify the residue by flash chromatography on silica gel eluting with 0-20% EtOAc/hexanes followed by flash chromatography on silica gel eluting with CHCl3 to afford the title compound (2.69 g, 56%). MS (IS) 322 (M+1)+. Heat to reflux under N2 overnight wash with saturated NaHCO3 solution, brine, and backextract from each aqueous layer with EtOAc Dry concentrate

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Add THF (125 mL, anhydrous) to a sealed vessel containing 5-thiocarbamoyl-pentanoic acid methyl ester (7.25 g, 41.4 mmol) and 2-bromo-2′-methoxyacetophenone (9.48 g, 41.4 mmol). Flush vessel with N2, seal, and heat at 80° C. overnight. Cool to room temperature, add EtOAc, wash with saturated aqueous NaHCO3 solution, brine, and backextract from each aqueous layer with EtOAc. Dry combined organic layers over MgSO4 and concentrate to get 18 grams of purple residue. Adsorb on SiO2 and purify the residue by flash chromatography on silica gel eluting with 0-20% EtOAc/hexanes to afford the title compound (9.7 g, 77%). TLC (30% EtOAc/hexanes) Rf=0.38. MS (IS) 306 (M+1)+. Flush vessel with N2 seal Cool to room temperature add EtOAc wash with saturated aqueous NaHCO3 solution, brine, and backextract from each aqueous layer with EtOAc Dry concentrate

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

Procedure: Add THF (50 mL, anhydrous) to a roundbottom flask containing 5-thiocarbamoyl-pentanoic acid methyl ester (2.63 g, 15.0 mmol) and 2-bromo-1-(2-hydroxy-4-methoxy-phenyl)-ethanone (4.90 g, 15.0 mmol, 75% pure). Heat to reflux under N2 overnight. Cool to room temperature, add EtOAc, wash with saturated NaHCO3 solution, brine, and backextract from each aqueous layer with EtOAc. Dry combined organic layers over MgSO4 and concentrate to get 8 grams of a yellow solid. Adsorb on SiO2 and purify the residue by flash chromatography on silica gel eluting with 0-20% EtOAc/hexanes followed by flash chromatography on silica gel eluting with CHCl3 to afford the title compound (2.69 g, 56%). MS (IS) 322 (M+1)+. Heat to reflux under N2 overnight wash with saturated NaHCO3 solution, brine, and backextract from each aqueous layer with EtOAc Dry concentrate

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Add THF (125 mL, anhydrous) to a sealed vessel containing 5-thiocarbamoyl-pentanoic acid methyl ester (7.25 g, 41.4 mmol) and 2-bromo-2′-methoxyacetophenone (9.48 g, 41.4 mmol). Flush vessel with N2, seal, and heat at 80° C. overnight. Cool to room temperature, add EtOAc, wash with saturated aqueous NaHCO3 solution, brine, and backextract from each aqueous layer with EtOAc. Dry combined organic layers over MgSO4 and concentrate to get 18 grams of purple residue. Adsorb on SiO2 and purify the residue by flash chromatography on silica gel eluting with 0-20% EtOAc/hexanes to afford the title compound (9.7 g, 77%). TLC (30% EtOAc/hexanes) Rf=0.38. MS (IS) 306 (M+1)+. Flush vessel with N2 seal Cool to room temperature add EtOAc wash with saturated aqueous NaHCO3 solution, brine, and backextract from each aqueous layer with EtOAc Dry concentrate

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

Procedure: Add THF (50 mL, anhydrous) to a roundbottom flask containing 5-thiocarbamoyl-pentanoic acid methyl ester-(2.63 g, 15.0 mmol) and 2-bromo-1-(2-hydroxy-4-methoxy-phenyl)-ethanone (4.90 g, 15.0 mmol, 75% pure). Heat to reflux under N2 overnight. Cool to room temperature, add EtOAc, wash with saturated NaHCO3 solution, brine, and backextract from each aqueous layer with EtOAc. Dry combined organic layers over MgSO4 and concentrate to get 8 grams of a yellow solid. Adsorb on SiO2 and purify the residue by flash chromatography on silica gel eluting with 0-20% EtOAc/hexanes followed by flash chromatography on silica gel eluting with CHCl3 to afford the title compound (2.69 g, 56%). MS (IS) 322 (M+1)+. Heat to reflux under N2 overnight wash with saturated NaHCO3 solution, brine, and backextract from each aqueous layer with EtOAc Dry concentrate

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Add THF (125 mL, anhydrous) to a sealed vessel containing 5-thiocarbamoyl-pentanoic acid methyl ester (7.25 g, 41.4 mmol) and 2-bromo-2′-methoxyacetophenone (9.48 g, 41.4 mmol). Flush vessel with N2, seal, and heat at 80° C. overnight. Cool to room temperature, add EtOAc, wash with saturated aqueous NaHCO3 solution, brine, and backextract from each aqueous layer with EtOAc. Dry combined organic layers over MgSO4 and concentrate to get 18 grams of purple residue. Adsorb on SiO2 and purify the residue by flash chromatography on silica gel eluting with 0-20% EtOAc/hexanes to afford the title compound (9.7 g, 77%). TLC (30% EtOAc/hexanes) Rf=0.38. MS (IS) 306 (M+1)+. Flush vessel with N2 seal Cool to room temperature add EtOAc wash with saturated aqueous NaHCO3 solution, brine, and backextract from each aqueous layer with EtOAc Dry concentrate

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

Procedure: Add THF (50 mL, anhydrous) to a roundbottom flask containing 5-thiocarbamoyl-pentanoic acid methyl ester (2.63 g, 15.0 mmol) and 2-bromo-1-(2-hydroxy-4-methoxy-phenyl)-ethanone (4.90 g, 15.0 mmol, 75% pure). Heat to reflux under N2 overnight. Cool to room temperature, add EtOAc, wash with saturated NaHCO3 solution, brine, and backextract from each aqueous layer with EtOAc. Dry combined organic layers over MgSO4 and concentrate to get 8 grams of a yellow solid. Adsorb on SiO2 and purify the residue by flash chromatography on silica gel eluting with 0-20% EtOAc/hexanes followed by flash chromatography on silica gel eluting with CHCl3 to afford the title compound (2.69 g, 56%). MS (IS) 322 (M+1)+. Heat to reflux under N2 overnight wash with saturated NaHCO3 solution, brine, and backextract from each aqueous layer with EtOAc Dry concentrate

Conditions: temp:80.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Add THF (125 mL, anhydrous) to a sealed vessel containing 5-thiocarbamoyl-pentanoic acid methyl ester (7.25 g, 41.4 mmol) and 2-bromo-2′-methoxyacetophenone (9.48 g, 41.4 mmol). Flush vessel with N2, seal, and heat at 80° C. overnight. Cool to room temperature, add EtOAc, wash with saturated aqueous NaHCO3 solution, brine, and backextract from each aqueous layer with EtOAc. Dry combined organic layers over MgSO4 and concentrate to get 18 grams of purple residue. Adsorb on SiO2 and purify the residue by flash chromatography on silica gel eluting with 0-20% EtOAc/hexanes to afford the title compound (9.7 g, 77%). TLC (30% EtOAc/hexanes) Rf=0.38. MS (IS) 306 (M+1)+. Flush vessel with N2 seal Cool to room temperature add EtOAc wash with saturated aqueous NaHCO3 solution, brine, and backextract from each aqueous layer with EtOAc Dry concentrate