benzyl 3-hydroxy-2-(hydroxymethyl)-2-methylpropanoate

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: Benzyl 2,2-bis(methylol)propionate (BnMPA) (11.2 g, 0.05 mol) was dissolved in CH2Cl2 (150 mL) and pyridine (25 mL, 0.3 mol) and the solution was chilled to −75° C. with dry ice/acetone under N2 atmosphere. A solution of triphosgene (7.5 g, 25 mmol) in CH2Cl2 (150 mL) was added dropwise over 1 hours, and then the reaction mixture was allowed to warm to room temperature for 2 hours. The reaction was quenched by addition of saturated aqueous NH4Cl (75 mL), after which the organic layer was washed with 1 M aqueous HCl (3×100 mL), saturated aqueous NaHCO3 (1×100 mL), dried over MgSO4, filtered and evaporated. The resulting solid was recrystallized from ethyl acetate (15 mL) to give MTCOBn as a white solid (10.7 g, 86%). 1H NMR (400 MHz, CDCl3, 22° C.): delta 7.37 (m, 5H, PhH), 5.20 (s, 2H, —OCH2Ph), 4.69 (d, 2H, —CH2OCOO), 4.23 (d, 2H, —CH2OCOO), 1.31 (s, 3H, —CH3). The reaction was quenched by addition of saturated aqueous NH4Cl (75 mL) after which the organic layer was washed with 1 M aqueous HCl (3×100 mL), saturated aqueous NaHCO3 (1×100 mL) dried over MgSO4 filtered evaporated The resulting solid was recrystallized from ethyl acetate (15 mL)

Conditions: temp:100.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture of 2,2-bis(methylol)propionic acid (bisMPA) (18.0 g, 0.134 mol), KOH (85% assay; 8.9 g, 0.135 mol), and DMF (100 mL) was heated to 100° C. for 1 hour (the reaction mixture became a homogenous solution after 0.5 hour reaction). Benzyl bromide (27.6 g, 0.162 mol) was added to the warm solution under stirring, and the reaction was continued at 100° C. for 16 hours. The reaction mixture was cooled down and the solvent was removed under vacuum. Ethyl acetate (120 mL), hexanes (120 mL), and water (80 mL) were added to the residue. The organic layer was retained, washed with water (80 mL), dried over MgSO4 and evaporated. The resulting solid was recrystallized from toluene (30 mL) to give pure benzyl 2,2-bis(methylol)propionate (BnMPA) (19.5 g, 65%). 1H NMR (400 MHz, CDCl3, 22° C.): delta 7.38 (m, 5H, PhH), 5.19 (s, 2H, —OCH2Ph), 3.94 (d, 2H, —CH2OH), 3.73 (d, 2H, —CH2OH), 1.12 (s, 3H, —CH3). after 0.5 hour reaction) The reaction mixture was cooled down the solvent was removed under vacuum Ethyl acetate (120 mL), hexanes (120 mL), and water (80 mL) were added to the residue washed with water (80 mL) dried over MgSO4 evaporated The resulting solid was recrystallized from toluene (30 mL)