(1S)-7-fluoro-1,2,3,4-tetrahydronaphthalen-1-ol

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

実験手順: DBU (27.1 mL, 180.5 mmol, 3 equiv.) was added to a solution of (S)-7-Fluoro-1,2,3,4-tetrahydronaphthalen-1-ol (10 g, 60.2 mmol, 1 equiv.) in toluene (300 mL). The resulted dark red solution was cooled in ice bath. Diphenylphosphoryl azide (38.6 mL, 180.6 mmol, 3 equiv) was added drop-wise within 30 min. The reaction solution was slowly brought to RT and stirred overnight. TLC was checked and showed no more SM. The reaction was diluted with methylene chloride (200 mL). The methylene chloride layer was washed with saturated NaHCO3, brine, water, saturated NH4Cl, and brine. The organic layer was separated and dried (Na2SO4), evaporated under reduced pressure to give a dark-red syrup which was purified on ISCO (80 g column, 0-2% EtOAc-hexane) to give a colorless oil product (7.9 g, 70%). 1H NMR (400 MHz, CDCl3) δ 7.07-7.11 (m, 1H), 7.02 (dd, 1H), 6.91-6.96 (m, 1H), 4.51 (t, 1H), 2.69-2.86 (m, 2H), 1.76-2.05 (m, 4H). The resulted dark red solution was cooled in ice bath was slowly brought to RT The methylene chloride layer was washed with saturated NaHCO3, brine, water, saturated NH4Cl, and brine The organic layer was separated dried (Na2SO4) evaporated under reduced pressure to give a dark-red syrup which was purified on ISCO (80 g column, 0-2% EtOAc-hexane)

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

実験手順: To an ice bath-cooled triethylamine (37.6 mL, 270.5 mmol, 7.4 equiv.) was added drop-wise formic acid (10.4 mL, 270.5 mmol, 7.4 equiv). The reaction solution was stirred at RT for 20 min. 7-Fluoro-3,4-dihydronaphthalen-1(2H)-one (6.0 g, 36.6 mmol, 1 equiv.) and Noyori(S,S) catalyst (560 mg, 2.5 mol %, prepared according to lit. 1, were added. Most was dissolved. DMF (10 mL) was added to make the reaction homogeneous. The reaction turned to dark red and was stirred at 40° C. overnight. TLC was checked and showed no more starting material. The solvents were removed by evaporation. The residue was mixed with water (100 mL) and stirred for 30 min to result a red solid, which was collected on funnel and washed with water and small amount of cold EtOH, then was dried in vacuo overnight. A red solid product (10.1 g, 100%) was obtained. 1H NMR (400 MHz, DMSO-d6) δ 7.16 (dd, 1H), 7.08 (t, 1H), 6.86-6.97 (m, 1H), 5.25 (d, 1H), 4.53 (q, 1H), 2.58-2.67 (m, 2H), 1.82-1.90 (m, 2H), 1.59-1.70 (m, 2H). were added Most was dissolved was stirred at 40° C. overnight The solvents were removed by evaporation The residue was mixed with water (100 mL) stirred for 30 min to result a red solid, which was collected on funnel washed with water and small amount of cold EtOH was dried in vacuo overnight