(3-Bromo-5-iodophenyl)methanol

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To methyl 5-bromo-3-iodobenzoate (Step A above) (5.01 g, 0.015 mole) in anhydrous methylene chloride (100 mL) at -78° C., was added dropwise minutes, diisobutylaluminum hydride (5.50 mL, 0.03 mole). The mixture was stirred for 1 hour then allowed to warm to 0° C. The reaction solution was poured into 600 mL, chilled 3N HCl and extracted 3× with methylene chloride (150 mL). The organic layers were combined, dried over MgSO4 and concentrated under vacuum to yield 5-bromo-3-iodobenzyl alcohol (4.54 g) as a white solid. MP=110-112° C. MS and NMR were consistent with the desired structure. The reaction solution was poured into 600 mL extracted 3× with methylene chloride (150 mL) dried over MgSO4 concentrated under vacuum

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of (3-bromo-5-iodophenyl)methanol from the previous step (1.0 eq.) and Dess-Martin periodinane (1.18 eq.) was stirred at RT in dichloromethane (0.1 M) for 45 min. The reaction mixture was diluted with ether, filtered through a plug of SiO2, and the silica washed with a 3:1 (v/v) mixture of hexanes:EtOAc. The filtrate was concentrated in vacuo and passed again through a plug of SiO2, eluting with a 3:1 (v/v) mixture of hexanes:EtOAc to afford the title compound as a light yellow solid. filtered through a plug of SiO2 the silica washed with a 3:1 (v/v) mixture of hexanes The filtrate was concentrated in vacuo eluting with a 3:1 (v/v) mixture of hexanes

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 3-bromo-5-iodobenzoic acid (1.0 eq.) in THF (0.2 M) at RT was added borane-methyl sulfide complex (1.5 eq). After 3 days of stirring at RT, the reaction mixture was quenched cautiously with 2 N aq. HCl and extracted with ether. The combined organic extracts were washed with 1 N aq. NaOH, water and brine, dried over MgSO4 and filtered. Concentration of the filtrate in vacuo afforded the title compound as a colorless oil. the reaction mixture was quenched cautiously with 2 N aq. HCl extracted with ether The combined organic extracts were washed with 1 N aq. NaOH, water and brine dried over MgSO4 filtered

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To methyl 5-bromo-3-iodobenzoate (Step A above) (5.01 g, 0.015 mole) in anhydrous methylene chloride (100 mL) at -78° C., was added dropwise minutes, diisobutylaluminum hydride (5.50 mL, 0.03 mole). The mixture was stirred for 1 hour then allowed to warm to 0° C. The reaction solution was poured into 600 mL, chilled 3N HCl and extracted 3× with methylene chloride (150 mL). The organic layers were combined, dried over MgSO4 and concentrated under vacuum to yield 5-bromo-3-iodobenzyl alcohol (4.54 g) as a white solid. MP=110-112° C. MS and NMR were consistent with the desired structure. The reaction solution was poured into 600 mL extracted 3× with methylene chloride (150 mL) dried over MgSO4 concentrated under vacuum

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of (3-bromo-5-iodophenyl)methanol from the previous step (1.0 eq.) and Dess-Martin periodinane (1.18 eq.) was stirred at RT in dichloromethane (0.1 M) for 45 min. The reaction mixture was diluted with ether, filtered through a plug of SiO2, and the silica washed with a 3:1 (v/v) mixture of hexanes:EtOAc. The filtrate was concentrated in vacuo and passed again through a plug of SiO2, eluting with a 3:1 (v/v) mixture of hexanes:EtOAc to afford the title compound as a light yellow solid. filtered through a plug of SiO2 the silica washed with a 3:1 (v/v) mixture of hexanes The filtrate was concentrated in vacuo eluting with a 3:1 (v/v) mixture of hexanes

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 3-bromo-5-iodobenzoic acid (1.0 eq.) in THF (0.2 M) at RT was added borane-methyl sulfide complex (1.5 eq). After 3 days of stirring at RT, the reaction mixture was quenched cautiously with 2 N aq. HCl and extracted with ether. The combined organic extracts were washed with 1 N aq. NaOH, water and brine, dried over MgSO4 and filtered. Concentration of the filtrate in vacuo afforded the title compound as a colorless oil. the reaction mixture was quenched cautiously with 2 N aq. HCl extracted with ether The combined organic extracts were washed with 1 N aq. NaOH, water and brine dried over MgSO4 filtered

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 3-bromo-5-iodobenzoic acid (1.0 eq.) in THF (0.2 M) at RT was added borane-methyl sulfide complex (1.5 eq). After 3 days of stirring at RT, the reaction mixture was quenched cautiously with 2 N aq. HCl and extracted with ether. The combined organic extracts were washed with 1 N aq. NaOH, water and brine, dried over MgSO4 and filtered. Concentration of the filtrate in vacuo afforded the title compound as a colorless oil. the reaction mixture was quenched cautiously with 2 N aq. HCl extracted with ether The combined organic extracts were washed with 1 N aq. NaOH, water and brine dried over MgSO4 filtered

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To methyl 5-bromo-3-iodobenzoate (Step A above) (5.01 g, 0.015 mole) in anhydrous methylene chloride (100 mL) at -78° C., was added dropwise minutes, diisobutylaluminum hydride (5.50 mL, 0.03 mole). The mixture was stirred for 1 hour then allowed to warm to 0° C. The reaction solution was poured into 600 mL, chilled 3N HCl and extracted 3× with methylene chloride (150 mL). The organic layers were combined, dried over MgSO4 and concentrated under vacuum to yield 5-bromo-3-iodobenzyl alcohol (4.54 g) as a white solid. MP=110-112° C. MS and NMR were consistent with the desired structure. The reaction solution was poured into 600 mL extracted 3× with methylene chloride (150 mL) dried over MgSO4 concentrated under vacuum

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of (3-bromo-5-iodophenyl)methanol from the previous step (1.0 eq.) and Dess-Martin periodinane (1.18 eq.) was stirred at RT in dichloromethane (0.1 M) for 45 min. The reaction mixture was diluted with ether, filtered through a plug of SiO2, and the silica washed with a 3:1 (v/v) mixture of hexanes:EtOAc. The filtrate was concentrated in vacuo and passed again through a plug of SiO2, eluting with a 3:1 (v/v) mixture of hexanes:EtOAc to afford the title compound as a light yellow solid. filtered through a plug of SiO2 the silica washed with a 3:1 (v/v) mixture of hexanes The filtrate was concentrated in vacuo eluting with a 3:1 (v/v) mixture of hexanes

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 3-bromo-5-iodobenzoic acid (1.0 eq.) in THF (0.2 M) at RT was added borane-methyl sulfide complex (1.5 eq). After 3 days of stirring at RT, the reaction mixture was quenched cautiously with 2 N aq. HCl and extracted with ether. The combined organic extracts were washed with 1 N aq. NaOH, water and brine, dried over MgSO4 and filtered. Concentration of the filtrate in vacuo afforded the title compound as a colorless oil. the reaction mixture was quenched cautiously with 2 N aq. HCl extracted with ether The combined organic extracts were washed with 1 N aq. NaOH, water and brine dried over MgSO4 filtered