1,8-Diazabicyclo(5.4.0)undec-7-ene → HCID 86761092, compound

Participants

Reaction Steps

Methyl (E)-2-diazo-3-pentenoate (5) was prepared using the scheme set forth in FIG. 7A. To a stirred solution of trans-pent-3-enoic acid (3.0 g, 30.0 mmol) in methanol (20 mL) was added concentrated H2SO4 (1 mL). The reaction mixture was stirred for 12 h at room temperature and then slowly neutralized with saturated sodium bicarbonate (NaHCO3). The aqueous layer was extracted with dichloromethane, and the combined organic layers were washed with brine and dried (Na2SO4). The solvent was removed under reduced pressure, and the remaining clear oil (3.30 g, 96% yield) was used for the next step, without further purification. To a stirred solution of methyl trans-pent-3-enoate (1.0 g, 8.77 mmol) and p-ABSA (3.15 g, 13.1 mmol) in CH3CN (20 mL) cooled to 0° C., was added DBU (2.66 g, 17.5 mmol) in one portion. p-ABSA (p-acetamidobenzenesulfonyl azide) was prepared using the procedure outlined in Baum et al., Synth. Commun., 17:1709ff (1987), which is hereby incorporated by reference. The reaction mixture was allowed to warm to room temperature over 7 h then quenched with saturated ammonium chloride (NH4Cl). The aqueous layer was extracted with diethyl ether, and the combined organic layers were washed with brine and dried (Na2SO4). The solvent was removed under reduced pressure and the residue was purified by flash chromatography (SiO2, pentane) to give methyl (E)-2-diazo-3-pentenoate (5) (0.80 g, 65% yield) as an orange oil, which was stored in pentane below −10° C. until ready for use. The spectroscopic data are consistent with previously reported data (Davies et al., J. Org. Chem., 57:3186ff (1992), which is hereby incorporated by reference).

Provenance & Evidence