(3aR,4R,5R,6aS)-4-((E)-4-(3-Chlorophenoxy)-3-oxobut-1-en-1-yl)-2-oxohexahydro-2H-cyclopenta[b]furan-5-yl benzoate → (3aR,4R,5R,6aS)-5-(Benzoyloxy)-4-[(E)-(3R)-4-(3-chlorophenoxy)-3-hydroxy-1-butenyl]-hexahydro-2H-cyclopenta[b]furan-2-one

HRID 1940265Notes

Reaction equation

HRID 1940265 reaction equation
[C:1]([O:9][C@@H:10]1[CH2:18][C@@H:13]2[O:14][C:15](=[O:17])[CH2:16][C@@H:12]2[C@H:11]1/[CH:19]=[CH:20]/[C:21](=[O:31])[CH2:22][O:23][C:24]1[CH:29]=[CH:28][CH:27]=[C:26]([Cl:30])[CH:25]=1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.B(Cl)([C@H]1[C@@H](C)[C@H]2C(C)(C)[C@H](C2)C1)[C@H]1[C@@H](C)[C@H]2C(C)(C)[C@H](C2)C1>C1COCC1>[C:1]([O:9][C@@H:10]1[CH2:18][C@@H:13]2[O:14][C:15](=[O:17])[CH2:16][C@@H:12]2[C@H:11]1/[CH:19]=[CH:20]/[C@@H:21]([OH:31])[CH2:22][O:23][C:24]1[CH:29]=[CH:28][CH:27]=[C:26]([Cl:30])[CH:25]=1)(=[O:8])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

4

Reactant 2

HCID 12041488(3aR,4R,5R,6aS)-4-((E)-4-(3-Chlorophenoxy)-3-oxobut-1-en-1-yl)-2-oxohexahydro-2H-cyclopenta[b]furan-5-yl benzoateHCID 86625794(-)-DIPCl

Product 1

HCID 12041489(3aR,4R,5R,6aS)-5-(Benzoyloxy)-4-[(E)-(3R)-4-(3-chlorophenoxy)-3-hydroxy-1-butenyl]-hexahydro-2H-cyclopenta[b]furan-2-oneYield 48.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 9.70 g (22.0 mmol) of enone 26 in 60 mL of THF at -23° C. was added dropwise a solution of 11.1 g (34.6 mmol) of (-)-DIPCl in 30 mL of THF. After 4h, the reaction was quenched at -23° C. by the dropwise addition of 5 mL of methanol, and was warmed to room temperature. The mixture was then poured into 200 mL of a 2:1 mixture of ethyl acetate: saturated NH4Cl, the layers were separated, and the aqueous phase was extracted with 2 X 100 mL portions of ethyl acetate. The combined organic layers were dried over MgSO4, concentrated, and the residue was flash chromatographed on a 33 cm tall×76 mm diameter silica gel column eluting with 3:2 v/v ethyl acetate:hexanes to afford 4.7 g (48%) of 27 as a white solid, m.p. 101.0°-102.5° C. 1H NMR δ 8.05-7.95 (m, 2H), 7.62-7.40 (m, 3H), 7.18 (t, J=8.0 Hz, 1H), 7.0-6.92 (m, 1H), 6.85 (t, J=2.1 Hz, 1H), 6.77-6.70 (m, 1H, 5.85 (d of d, J=6.2, 15.5 Hz, 1H), 5.72 (d of d, J=4.5, 15.5 Hz, 1H), 5.30 (q, J=5.8 Hz, 1H), 5.12-5.04 (m, 1H), 4.58-4.48 (m, 1H), 3.92 (d of d, J=3.5, 9.3 Hz, 1H), 3.80 (d of d, J=7.3, 9.4 Hz, 1H), 2.9-2.2 (m, 8H).

Workup

  1. customAfter 4h, the reaction was quenched at -23° C. by the dropwise addition of 5 mL of methanol
  2. additionThe mixture was then poured into 200 mL of a 2:1 mixture of ethyl acetate
  3. customsaturated NH4Cl, the layers were separated
  4. extractionthe aqueous phase was extracted with 2 X 100 mL portions of ethyl acetate
  5. dry with materialThe combined organic layers were dried over MgSO4
  6. concentrationconcentrated
  7. customchromatographed on a 33 cm tall×76 mm diameter silica gel column
  8. washeluting with 3:2 v/v ethyl acetate

Sources & evidence

ORD record
ord-5f505320755b4f1c92e3e656f75d42c3
Source dataset
uspto-grants-1997_12
Patent number
US05698733

Reaction notes

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