2-methylidenepropane-1,3-diol

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of t-butyldiphenylsilylchloride (45 g, 165 mmol) in anhydrous dichloromethane (60 ml) is added dropwise to a stirred solution of 2-hydroxymethyl-2-propene-1-ol (12 g, 165 mmol) triethylamine (27.5 ml) and 4-dimethylaminopyridine (2 g) in anhydrous dichloromethane (300 ml) at 0° C. Then, the mixture is stirred at 20° C. overnight, washed with a saturated solution of ammonium chloride and brine. The title product is obtained by flash chromatography on silica gel (19.4 g, 40%). washed with a saturated solution of ammonium chloride and brine

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

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

実験手順: To a solution of trityl chloride (4.05 g; 14.3 mmol) and 2-methylenepropane-1,3-diol (1.20 mL; 14.3 mmol) in dry CH2Cl2 (20 mL) was added triethylamine (4.0 mL; 28.5 mmol) slowly at room temperature. The reaction was stirred at room temperature for 1 h and then ethyl acetate (100 mL) and saturated aqueous NaHCO3 (30 mL) were added. The organic layer was separated and washed by saturated aqueous NaHCO3 and NaCl respectively, and dried over anhydrous Na2SO4. After evaporation of the solvent, the residue was purified by flash column chromatography over silica gel using ethyl acetate-hexane (1:10.5) as the eluent to afford 10 as white solid (2.89 g; 62% yield): 1H NMR (400 MHz, CDCl3) δ 7.42-7.48 (m, 6H, six of ArH), 7.27-7.33 (m, 6H, six of ArH), 7.20-7.27 (m, 3H, three of ArH), 5.26 (s, 1H, one of C═CH2), 5.17 (s, 1H, one of C═CH2), 4.13 (d, J=6.1 Hz, 2H, CH2OH), 3.70 (s, 2H, Ph3COCH2), 1.72 (t, J=6.1 Hz, 1H, CH2OH); 13C NMR (100 MHz, CDCl3) δ 145.4, 143.6, 128.3, 127.6, 126.8, 111.6, 87.0, 65.3, 64.5, (8). The organic layer was separated washed by saturated aqueous NaHCO3 and NaCl respectively dried over anhydrous Na2SO4 After evaporation of the solvent the residue was purified by flash column chromatography over silica gel

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

実験手順: To a solution of trityl chloride (4.05 g; 14.3 mmol) and 2-methylenepropane-1,3-diol (1.20 mL; 14.3 mmol) in dry CH2Cl2 (20 mL) was added triethylamine (4.0 mL; 28.5 mmol) slowly at room temperature. The reaction was stirred at room temperature for 1 h and then ethyl acetate (100 mL) and saturated aqueous NaHCO3 (30 mL) were added. The organic layer was separated and washed by saturated aqueous NaHCO3 and NaCl respectively, and dried over anhydrous Na2SO4. After evaporation of the solvent, the residue was purified by flash column chromatography over silica gel using ethyl acetate-hexane (1:10.5) as the eluent to afford 10 as white solid (2.89 g; 62% yield): 1H NMR (400 MHz, CDCl3) δ 7.42-7.48 (m, 6H, six of ArH), 7.27-7.33 (m, 6H, six of ArH), 7.20-7.27 (m, 3H, three of ArH), 5.26 (s, 1H, one of C═CH2), 5.17 (s, 1H, one of C═CH2), 4.13 (d, J=6.1 Hz, 2H, CH2OH), 3.70 (s, 2H, Ph3COCH2), 1.72 (t, J=6.1 Hz, 1H, CH2OH); 13C NMR (100 MHz, CDCl3) δ 145.4, 143.6, 128.3, 127.6, 126.8, 111.6, 87.0, 65.3, 64.5, (8). The organic layer was separated washed by saturated aqueous NaHCO3 and NaCl respectively dried over anhydrous Na2SO4 After evaporation of the solvent the residue was purified by flash column chromatography over silica gel

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

実験手順: Prepared as in Example 166d from 2,6-dinitrobenzonitrile and 2-methylenepropane-1,3-diol in 55% yield as a white solid. 1H-NMR (400 MHz, DMSO-d6) δ 7.93 (dd, J=8.4 Hz, J=0.8 Hz, 1H), 7.89 (t, J=8.0 Hz, 1H), 7.73 (dd, J=7.6 Hz, J=0.8 Hz, 1H), 5.23-5.29 (m, 2H), 5.03 (t, J=5.6 Hz, 1H), 4.85 (s, 2H), 4.06 (d, J=5.2 Hz, 2H). |ΠατAππ1009—Λ1|ZZMΠTAΓ|

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

実験手順: Prepared as in Example 166d from 2,6-dinitrobenzonitrile and 2-methylenepropane-1,3-diol in 55% yield as a white solid. 1H-NMR (400 MHz, DMSO-d6) δ 7.93 (dd, J=8.4 Hz, J=0.8 Hz, 1H), 7.89 (t, J=8.0 Hz, 1H), 7.73 (dd, J=7.6 Hz, J=0.8 Hz, 1H), 5.23-5.29 (m, 2H), 5.03 (t, J=5.6 Hz, 1H), 4.85 (s, 2H), 4.06 (d, J=5.2 Hz, 2H). |ΠατAππ1009—Λ1|ZZMΠTAΓ|

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

実験手順: To a dry flask containing sodium hydride (2.270 g, 56.75 mmol) in THF (150 mL) under N2 at 0° C. was added slowly 2-methylenepropane-1,3-diol (5 g, 56.75 mmol). The reaction was warmed to room temperature and stirred 45 min. TBS-Cl (8.55 g, 56.75 mmol) was added in one batch and stirring was continued for another 45 min, until complete by TLC. To the reaction was added water and the mixture was extracted three times with EtOAc and washed with brine. The organics were dried over magnesium sulfate, filtered and concentrated at −10-15° C. Silica gel chromatography (20%-50% EtOAc/Hex) afforded the title compound (11.36 g, 99%) as a clear oil. stirring was continued for another 45 min the mixture was extracted three times with EtOAc washed with brine The organics were dried over magnesium sulfate filtered concentrated at −10-15° C