(1R)-1-(4-bromophenyl)ethanamine

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

Procedure: A mixture of 2.0 g (10.0 mmol) (R)-1-(4-bromo-phenyl)-ethylamine and 30 ml toluene (dry) was cooled to 0° C. Thereafter, 5.2 ml (30.0 mmol) of di-iso-propylethylamine was added drop-wise, followed by the addition of 7.4 ml (85 mmol) allyl bromide. The resulting mixture was warmed to room temperature and then heated to 95° C. for 2.5 hours. The mixture was filtered. The precipitate was then washed with toluene and the filtrate and washings were combined and then concentrated in vacuo to give a reddish-brown oil. Chromatography on silica gel using 15% ethyl acetate/hexanes gave 2.76 g (99%) oil. The resulting mixture was warmed to room temperature heated to 95° C. for 2.5 hours The mixture was filtered The precipitate was then washed with toluene concentrated in vacuo to give a reddish-brown oil

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

Procedure: A mixture of 2.0 g (10.0 mmol) (R)-1-(4-bromo-phenyl)-ethylamine and 30 ml toluene (dry) was cooled to 0° C. Thereafter, 5.2 ml (30.0 mmol) of di-iso-propylethylamine was added drop-wise, followed by the addition of 7.4 ml (85 mmol) allyl bromide. The resulting mixture was warmed to room temperature and then heated to 95° C. for 2.5 hours. The mixture was filtered. The precipitate was then washed with toluene and the filtrate and washings were combined and then concentrated in vacuo to give a reddish-brown oil. Chromatography on silica gel using 15% ethyl acetate/hexanes gave 2.76 g (99%) oil. The resulting mixture was warmed to room temperature heated to 95° C. for 2.5 hours The mixture was filtered The precipitate was then washed with toluene concentrated in vacuo to give a reddish-brown oil

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of (R)-(+)-1-(4-bromophenyl)ethylamine (1 g, 5 mmol), in anhydrous CH2Cl2 (10 mL) under argon were added ethane sulfonyl chloride (0.57 mL, 5.99 mmol) and Pyridine (0.60 mL, 7.5 mmol). The resulting solution was stirred at 25° C. for 3 hrs. The reaction mixture was quenched with 1N HCl and extracted with EtOAc (3×10 mL). The organic phase was washed with brine (50 mL), dried over Na2SO4 and evaporated. The residue was purified by flash column chromatography (80% EtOAc in hexanes) to give the product (0.40 g, 58%) as a white solid. 1H NMR (CDCl3) δ: 1.23 (t, J=7.5 Hz, 3 H), 1.52 (d, J=6.8 Hz, 3 H), 2.77 (q, J=14, 7.5 Hz, 2 H), 4.61–4.72 (m, 2 H), 7.24 (d, J=8.3 Hz, 2 H), 7.51 (d, J=8.3 Hz, 2 H). ESIMS (MH+): 293. The reaction mixture was quenched with 1N HCl extracted with EtOAc (3×10 mL) The organic phase was washed with brine (50 mL) dried over Na2SO4 evaporated The residue was purified by flash column chromatography (80% EtOAc in hexanes)

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of (R)-(+)-1-(4-bromophenyl)ethylamine (1 g, 5 mmol), in anhydrous CH2Cl2 (10 mL) under argon were added ethane sulfonyl chloride (0.57 mL, 5.99 mmol) and Pyridine (0.60 mL, 7.5 mmol). The resulting solution was stirred at 25° C. for 3 hrs. The reaction mixture was quenched with 1N HCl and extracted with EtOAc (3×10 mL). The organic phase was washed with brine (50 mL), dried over Na2SO4 and evaporated. The residue was purified by flash column chromatography (80% EtOAc in hexanes) to give the product (0.40 g, 58%) as a white solid. 1H NMR (CDCl3) δ: 1.23 (t, J=7.5 Hz, 3 H), 1.52 (d, J=6.8 Hz, 3 H), 2.77 (q, J=14, 7.5 Hz, 2 H), 4.61–4.72 (m, 2 H), 7.24 (d, J=8.3 Hz, 2 H), 7.51 (d, J=8.3 Hz, 2 H). ESIMS (MH+): 293. The reaction mixture was quenched with 1N HCl extracted with EtOAc (3×10 mL) The organic phase was washed with brine (50 mL) dried over Na2SO4 evaporated The residue was purified by flash column chromatography (80% EtOAc in hexanes)

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of (R)-(+)-1-(4-bromophenyl)ethylamine (0.5 g, 2.49 mmol), in anhydrous CH2Cl2 (5 mL) under argon were added methane sulfonyl chloride (0.23 mL, 2.99 mmol) and pyridine (0.30 mL, 3.73 mmol). The resulting solution was stirred at 25° C. for 3 hrs. The reaction mixture was quenched with 1N HCl and extracted with EtOAc (30 mL). The organic phase was washed with brine (50 mL), dried over Na2SO4 and evaporated. The residue was purified by flash column chromatography (80% EtOAc in hexanes) to give the product (0.40 g, 58%) as a white solid. 1H NMR (CDCl3) δ: 1.52 (d, J=6.8 Hz, 3 H), 2.67 (s, 3 H), 4.61–4.72 (m, 2 H), 7.24 (d, J=8.3 Hz, 2 H), 7.51 (d, J=8.3 Hz, 2 H). ESIMS (MNa+): 279. The reaction mixture was quenched with 1N HCl extracted with EtOAc (30 mL) The organic phase was washed with brine (50 mL) dried over Na2SO4 evaporated The residue was purified by flash column chromatography (80% EtOAc in hexanes)

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of (R)-(+)-1-(4-bromophenyl)ethylamine (0.5 g, 2.49 mmol), in anhydrous CH2Cl2 (5 mL) under argon were added methane sulfonyl chloride (0.23 mL, 2.99 mmol) and pyridine (0.30 mL, 3.73 mmol). The resulting solution was stirred at 25° C. for 3 hrs. The reaction mixture was quenched with 1N HCl and extracted with EtOAc (30 mL). The organic phase was washed with brine (50 mL), dried over Na2SO4 and evaporated. The residue was purified by flash column chromatography (80% EtOAc in hexanes) to give the product (0.40 g, 58%) as a white solid. 1H NMR (CDCl3) δ: 1.52 (d, J=6.8 Hz, 3 H), 2.67 (s, 3 H), 4.61–4.72 (m, 2 H), 7.24 (d, J=8.3 Hz, 2 H), 7.51 (d, J=8.3 Hz, 2 H). ESIMS (MNa+): 279. The reaction mixture was quenched with 1N HCl extracted with EtOAc (30 mL) The organic phase was washed with brine (50 mL) dried over Na2SO4 evaporated The residue was purified by flash column chromatography (80% EtOAc in hexanes)

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

Procedure: The title compound was prepared as described in Step 1 of Example A(39), where 2-(4-bromophenyl)-2-methyl propionic acid was substituted for ethyl hydrogen malonate and ethyl amine was substituted for (R)-(+)-1-(4-bromophenyl)ethylamine on that example. Yield 82%.

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

Procedure: The title compound was prepared as described in Step 1 of Example A(39), where 2-(4-bromophenyl)-2-methyl propionic acid was substituted for ethyl hydrogen malonate and methyl amine was substituted instead of (R)-(+)-1-(4-bromophenyl)ethylamine on that example. Yield 84%.

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

Procedure: The title compound was prepared as described in Step 1 of Example A(39), where 2-(4-bromophenyl)-2-methyl propionic acid was substituted for ethyl hydrogen malonate and methyl amine was substituted instead of (R)-(+)-1-(4-bromophenyl)ethylamine on that example. Yield 84%.

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of (R)-(+)-1-(4-bromophenyl)ethylamine (0.5 g, 2.49 mmol), in anhydrous CH2Cl2 (5 mL) under argon were added methane sulfonyl chloride (0.23 mL, 2.99 mmol) and Pyridine (0.30 mL, 3.73 mmol). The resulting solution was stirred at 25° C. for 3 hrs. The reaction mixture was quenched with 1 N HCl and extracted with EtOAc (30 mL). The organic phase was washed with brine (50 mL), dried over Na2SO4 and evaporated. The residue was purified by flash column chromatography (80% EtOAc in hexanes) to give the product (0.40 g, 58%) as a white solid. The reaction mixture was quenched with 1 N HCl extracted with EtOAc (30 mL) The organic phase was washed with brine (50 mL) dried over Na2SO4 evaporated The residue was purified by flash column chromatography (80% EtOAc in hexanes)

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of (R)-(+)-1-(4-bromophenyl)ethylamine (0.5 g, 2.49 mmol), in anhydrous CH2Cl2 (5 mL) under argon were added methane sulfonyl chloride (0.23 mL, 2.99 mmol) and Pyridine (0.30 mL, 3.73 mmol). The resulting solution was stirred at 25° C. for 3 hrs. The reaction mixture was quenched with 1 N HCl and extracted with EtOAc (30 mL). The organic phase was washed with brine (50 mL), dried over Na2SO4 and evaporated. The residue was purified by flash column chromatography (80% EtOAc in hexanes) to give the product (0.40 g, 58%) as a white solid. The reaction mixture was quenched with 1 N HCl extracted with EtOAc (30 mL) The organic phase was washed with brine (50 mL) dried over Na2SO4 evaporated The residue was purified by flash column chromatography (80% EtOAc in hexanes)

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a stirred solution of (R)-(+)-1-(4-bromophenyl)ethylamine (0.5 g, 2.49 mmol) in anhydrous CH2Cl2 was added methyl isocyanate (0.15 mL, 2.49 mmol). The resulting solution was stirred at 25° C. overnight. CH2Cl2 was evaporate and residue partitioned between EtOAC and 1 N HCl. The organic layer was washed with H2O, brine and dried over Na2SO4. The solvent was removed in vacuo and the residue was purified by flash column chromatography (80% EtOAc in hexanes) to provide the desired product (0.60 g, 94%) as a white solid. CH2Cl2 was evaporate residue partitioned between EtOAC and 1 N HCl The organic layer was washed with H2O, brine dried over Na2SO4 The solvent was removed in vacuo the residue was purified by flash column chromatography (80% EtOAc in hexanes)