4-Toluenesulfonyl chloride → 2-(Tert-butoxy)ethyl 4-methylbenzenesulfonate

Participants

Reaction Steps

Dissolve ethylene glycol mono-tert-butyl ether (2.62 g, 22.17 mmol) and triethylamine (3.36 g, 11.02 mmol) in 40 mL methylene chloride at 0° C. Dissolve para-toluenesulfonyl chloride (4.2277 g, 22.17 mmol) in 10 mL methylene chloride and add it dropwise to the reaction. After 30 minutes raise the reaction to room temperature and allow it to stir for 17 hours. Dilute the reaction with methylene chloride and wash it with water (1×), 1N HCl (1×), saturated aqueous sodium hydrogen carbonate (1×) and brine (1×). Dry the organic layer with magnesium sulfate. Filter and remove the solvent in vacuo to give 4.6387 g of crude toluene-4-sulfonic acid 2-tert-butoxyethyl ester. Dissolve this crude material (1.2423 g, 4.56 mmol) and di-benzyl iminodicarboxylate (1.4385 g, 5.04 mmol) (see Synthesis, 1988, 992-994) in 20 mL acetonitrile. Add potassium tert-butoxide (575.9 mg, 5.13 mmol) to the reaction mixture and heat it to reflux for 24 hours. Cool the reaction to room temperature and remove the solvent in vacuo. Dissolve the residue in methylene chloride and wash it with water (1×) and brine (1×). Dry the organic layer with magnesium sulfate. Filter and remove the solvent in vacuo to give 1.9215 g of crude material. Purify via Biotage chromatography (EtOAc/Hexanes) to afford 387.8 mg of (2-tert-butoxyethyl)dicarbamic acid benzyl ester (22%). MS (ES): m/z 386.3 (M+H).

Provenance & Evidence