반응 #2649

ord-1ac771ea14f8470d9583f912bd68a7b3

반응 방정식

CCN(CC)CC
triethylamine
C=COC(C)=O
vinyl acetate
ClC(Cl)Cl
chloroform
CC(C)(C)O[C@H]1C=C[C@@H](O)C1
Cis-4-tert-butyloxy-cyclopent-2-enol
CC(=O)O[C@@H]1C=C[C@H](OC(C)(C)C)C1
(-)-acetic acid cis-4-tert-butyloxy-cyclopent-2-enyl ester
수율 50.0%

반응 조건

상세 조건
See reaction.notes.procedure_details.

후처리

  1. 1
    여과The reaction is then filtered through diatomaceous earth
  2. 2
    농축the filtrate is concentrated under vacuum
  3. 3
    기타The products are separated by chromatography on silica gel (10% to 20% ethyl acetate/hexane)

실험 절차

Cis-4-tert-butyloxy-cyclopent-2-enol (485 mg, 3.1 mmol, prepared in example 9) is dissolved in tert-butyl methyl ether (8.6 mL, anhydrous). To the solution is added triethylamine (0.7 eq), pancreatin (3 wt eq, available from Sigma Chemical Company), and vinyl acetate (5 eq). The reaction is allowed to stir for 17 hours at room temperature. The reaction is then filtered through diatomaceous earth and the filtrate is concentrated under vacuum. The products are separated by chromatography on silica gel (10% to 20% ethyl acetate/hexane) to provide (-)-acetic acid cis-4-tert-butyloxy-cyclopent-2-enyl ester (B, 50% yield, 76% ee), [α]D =-10.9°, (c=0.98, chloroform), 1H NMR (CDCl3) δ5.94 (d, 1H, J=5.5 Hz), 5.89 (d, 1H, J=5.5 Hz), 5.46 (appt, 1H, J=5.5 Hz), 4.52 (appt, 1H, J=5.5 Hz), 2.8 (m, 1H), 2.0 (s, 3H), 1.6 (d appt, 1H, J=4.8, 14 Hz), 1.22 (s, 9H); 13C NMR (CDCl3) δ171.2, 138.6, 131.6, 77.4, 77.2, 41, 28.7, 28.6, 21.4; IR (neat) νmax 2976, 1738, 1364, 1242, 1196, 1067, 1020 cm-1 ; CIMS m/e (% relative intensity) 199 (M+H+, 4), 139 (M+H+ -AcOH, 70), 83 (100), and (-)-cis-4-tert-butyloxy-cyclopent-2-enol (A, 194 mg, 40% yield, >98% ee), [α]D 17.2°, (c=1.09, chloroform) as a yellow oil.

출처

DOI: 10.6084/m9.figshare.5104873.v1특허: US05728899uspto-grants-1998_03