methyl (E)-3-(3-bromophenyl)prop-2-enoate

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

Procedure: A solution of trans-3-(3-bromophenyl)-2-propenoic acid (0.405 mol) in methanol (300 ml) was treated with conc. sulfuric acid (6.0 ml) and heated under reflux for 10 h. The cooled mixture was filtered to afford the title compound (46.14 g, 47%) as brilliant white crystals, m.p. 53°-55° C. (Found: C, 50.10; H, 3.58; Br; 33.21. C10 H9BrO2 requires C, 49.82; H, 3.76; Br, 33.14%); νmax (nujol)/cm-1 1730.5, 1715.0, 1644; δH (270 MHz) 3.81 (3H, s, OCH3); 6.43 (1H, d, 2-H, 3J2,3 =16.2 Hz); 7.25 (1H, t, 5'-H, Jo =7.8 Hz); 7.43 (1H, dt, 4'-H, Jo =7.9, Jm =1.0 Hz); 7.50 (1H, dt, 6'-H, Jo =7.9, Jm =1.0 Hz); 7.60 (1H, d, 3-H, 3J3,2 =16.2 Hz); 7.66 (1H, t, 2'-H, Jm =1.7 Hz). δC (67.8 MHz) 51.8 (OCH3); 123.0 (3'-C); 133.0 (4'-C); 136.4 (1'-C); 143.1 (3-C); 166.9 (CO2Me). Remaining signals lie in the range 119.3-130.7 ppm; m/z 242.0, 240.0 (46.67, 47.64, M+), 211.0, 209.0 (72.69, 74.00), 182.9, 180.9 (15.67, 16.83), 161.0 (4.19), 130.0 (9.44), 102.1 (100). heated under reflux for 10 h The cooled mixture was filtered

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

Procedure: A solution of trans-3-(3-bromophenyl)-2-propenoic acid (0.405 mol) in methanol (300 ml) was treated with conc. sulfuric acid (6.0 ml) and heated under reflux for 10 h. The cooled mixture was filtered to afford the title compound (46.14 g, 47%) as brilliant white crystals, m.p. 53-55° C. (Found: C, 50.10; H, 3.58; Br; 33.21. C10H9BrO2 requires C, 49.82; H, 3.76; Br, 33.14%); νmax (nujol)/cm−1 1730.5, 1715.0, 1644; δH (270 MHz) 3.81 (3H, s, OCH3); 6.43 (1H, d, 2-H, 3J2,3=16.2 Hz); 7.25 (1H, t, 5′-H, Jo=7.8 Hz); 7.43 (1H, dt, 4′-H, Jo=7.9, Jm=1.0 Hz); 7.50 (1H, dt, 6′-H, Jo=7.9, Jm=1.0 Hz); 7.60 (1H, d, 3-H, 3J3,2=16.2 Hz); 7.66 (1H, t, 2′-H, Jm=1.7 Hz). δc (67.8 MHz) 51.8 (OCH3); 123.0 (3′-C); 133.0 (4′-C); 136.4 (1′-C); 143.1 (3-C); 166.9 (CO2Me). Remaining signals lie in the range 119.3-130.7 ppm; m/z 242.0, 240.0 (46.67, 47.64, M+), 211.0, 209.0 (72.69, 74.00), 182.9, 180.9 (15.67, 16.83), 161.0 (4.19), 130.0 (9.44), 102.1 (100). heated under reflux for 10 h The cooled mixture was filtered

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

Procedure: Add benzyl-methoxymethyl-trimethylsilanyl-amine (14.7 g, 2.20 mmol) to a solution of trans-3-(3-bromo-phenyl)-acrylic acid methyl ester (10.0 g, 41.4 mmol) in methylene chloride (80 mL). Cool the mixture to 0° C. and stir for 10 min then add trifluoroacetic acid (0.92 mL, 12.4 mmol) and stir the mixture at 0° C. for an additional 4 h. Dilute the reaction mixture with water and extract with methylene chloride. Dry the combined organic phase over anhydrous sodium sulfate and concentrate under reduced pressure. Purify the residue by silica gel chromatography to provide 12 g (77%) of trans-1-benzyl-4-(3-bromo-phenyl)-pyrrolidine-3-carboxylic acid methyl ester. extract with methylene chloride Dry the combined organic phase over anhydrous sodium sulfate concentrate under reduced pressure Purify the residue by silica gel chromatography

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

Procedure: Add concentrated sulfuric acid (5.0 mL, 90 mmol) to a solution of 3-bromocinnamic acid (25.0 g, 110 mmol) in MeOH (250 mL). Heat the mixture to reflux for 5 h then cool to room temperature and concentrate under reduced pressure. Dilute the residue with water and extract with EtOAc. Concentrate the combined organic phase under reduced pressure and purify the residue by silica gel chromatography to provide 26 g of trans-3-(3-bromo-phenyl)-acrylic acid methyl ester. Heat the mixture to reflux for 5 h concentrate under reduced pressure Dilute the residue with water extract with EtOAc Concentrate the combined organic phase under reduced pressure purify the residue by silica gel chromatography

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

Procedure: The title compound was prepared from trans-3-(3-bromophenyl)-2-propenol by a sequence analogous to that described above for compound (9a) but using D-(-)-diethyl tartrate. Column chromatography (ethyl acetate--light petroleum (b.p. 40-60° C.), 3:7) provided the title compound (73%) as a pale yellow oil. Distilled at 160-185° C. at 0.1 mmHg. using a Kugelrohr short path distillation apparatus as a colourless oil; [α]D25 +37.6 (c=0.020 gml-1, CHCl3).

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

Procedure: A solution of trans-3-(3-bromophenyl)-2-propenoic acid (0.405 mol) in methanol (300 ml) was treated with conc. sulfuric acid (6.0 ml) and heated under reflux for 10 h. The cooled mixture was filtered to afford the title compound (46.14 g, 47%) as brilliant white crystals, m.p. 53-55° C. (Found: C, 50.10; H, 3.58; Br; 33.21. C10H9BrO2 requires C, 49.82; H, 3.76; Br, 33.14%); Vmax (nujol)/cm-1 1730.5, 1715.0, 1644; δH (270 MHz) 3.81 (3H, s, OCH3); 6.43 (1H, d, 2-H, 3J2,3 =16.2 Hz); 7.25 (1H, t, 5'-H, Jo =7.8 Hz); 7.43 (1H, dt, 4'-H, Jo =7.9, Jm =1.0 Hz); 7.50 (1H, dt, 6'-H, Jo =7.9, Jm =1.0 Hz); 7.60 (1H, d, 3-H, 3J3,2 =16.2 Hz); 7.66 (1H, t, 2'-H, Jm =1.7 Hz). δC (67.8 MHz) 51.8 (OCH3); 123.0 (3'-C); 133.0 (4'-C); 136.4 (1'-C); 143.1 (3-C); 166.9 (CO2Me). Remaining signals lie in the range 119.3-130.7 ppm; m/z 242.0, 240.0 (46.67, 47.64, M+), 211.0, 209.0 (72.69, 74.00), 182.9, 180.9 (15.67, 1683), 161.0 (4.19), 130.0 (9.44), 102.1 (100). heated under reflux for 10 h The cooled mixture was filtered