Benzyl Alcohol → HCID 11392118, compound

Participants

Reaction Conditions

Reaction Steps

Methyl (1S, 6R)-6-Benzyloxycarbonylaminocyclohex-3-enecarboxylate (2-4) was prepared according to the procedure of Ohno and co-workers4, that was successfully repeated by Appella et al.3 of the Gellman group. The monoester 2-3 (7.08 g, 38.4 mmol) was dissolved in acetone (125 mL) and the resulting solution cooled to 0° C. To this solution was added Et3N (7.0 mL, 50.2 mmol), followed by slow addition of ethyl chioroformate (4.77 mL, 49.9 mmol). Mixture was stirred at 0° C. for 15 minutes. In a separate flask, NaN3 (4 g, 61.5 mmol) was dissolved in Millipore water (35 mL), and this solution added to the reaction flask. The temperature was gradually raised to room temperature and stirring continued for 3 hours. The reaction mixture was diluted with water (123 mL) and the resulting solution extracted three times with diethyl ether (900 mL total). The organic extracts were dried over MgSO4, concentrated without heating, and put under vacuum for a few minutes to afford yellow oil. To this oil was added anhydrous benzene (97 mL), and the resulting solution refluxed under a nitrogen atmosphere for 3 hours. The solution was cooled to room temperature followed by the addition of benzyl alcohol (13.9 mL, 133.8 mmol). The resulting solution was refluxed under an atmosphere of nitrogen for 22 hours. A yellow solution containing droplets of another liquid on the bottom of the flask was formed. The solution was cooled to room temperature, and the solvent was then removed on a rotary evaporator to afford 22.1 g (82% yield of 2-4 based on 1H NMR) of yellow liquid being a mixture of 2-4 and benzyl alcohol: 1H NMR (300 MHz, CDCl3): δ 7.39-7.22 (m, ArH of 2-4 and BnOH), 5.67 (m, 2H, HC═CH), 5.45 (br d, J=9 Hz, 1H, NH), 5.06 (s, 2H, ArCH2) 4.64 (s, ArCH2 of BnOH), 4.23 (m, 1H, CHNHCbz), 3.66 (s, 3H, OCH3), 2.80 (m, 1H, CHCOOCH3), 2.57-2.43 (m, 1H), 2.42-2.25 (m, 2H), 2.23-2.10 (m, 1H).

Provenance & Evidence