تفاعل #2649

ord-1ac771ea14f8470d9583f912bd68a7b3

معادلة التفاعل

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
المردود 50.0%

المذيبات

ظروف التفاعل

الظروف التفصيلية
See reaction.notes.procedure_details.

المعالجة

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

الإجراء التجريبي

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.

المصدر

DOI: 10.6084/m9.figshare.5104873.v1براءة الاختراع: US05728899uspto-grants-1998_03