Triphenylphosphine → HCID 86653601, compound

Participants

Reaction Steps

A solution of methyl (4RS,6RS)-6-(4-chloro-3-(trifluoromethyl)phenyl)-4-(hydroxymethyl)-6-methylcyclohex-1-enecarboxylate (Example 7, Step 9; 38.2 mg, 0.105 mmol) in THF (0.8 mL) was treated sequentially with triphenylphosphine (83 mg, 0.316 mmol), hydrazoic acid (ca. 2M in benzene, 0.211 mL, 0.421 mmol) and diethyl azodicarboxylate (0.050 mL, 0.316 mmol). The resulting mixture was stirred at rt for 19.5 h and then an additional amount of triphenylphosphine (83 mg, 0.316 mmol), diethyl azodicarboxylate (0.050 mL, 0.316 mmol) and hydrazoic acid (ca. 2M in benzene, 0.211 mL, 0.421 mmol) were added. The resulting mixture was stirred for a total of 43 h. After this time, the mixture was concentrated under vacuum to yield a residue. The residue was purified by column chromatography on silica gel, eluting with 5-50% ethyl acetate-hexanes, to provide methyl (4RS,6RS)-4-(azidomethyl)-6-(4-chloro-3-(trifluoromethyl)-phenyl)-6-methylcyclohex-1-enecarboxylate (21 mg, 51%). Mass spectrum m/z 405.0 (M+NH4+). 1H NMR (400 MHz, CDCl3) δ 7.54 (d, J=2.4 Hz, 1 H), 7.40 (d, J=8.4 Hz, 1 H), 7.31 (dd, J=8.4, 2.4 Hz, 1 H), 7.25 (dd, J=5.5, 2.4 Hz, 1 H), 3.65 (s, 3 H), 3.17 (d, J=5.3 Hz, 2 H), 2.45 (m, 1 H), 2.01 (m, 1 H), 1.73 (m, 1 H), 1.66 (s, 3 H), 1.58 (m, 2 H).

Provenance & Evidence