Chlorobis((1S,2R,3S,5S)-2,6,6-trimethylbicyclo(3.1.1)hept-3-yl)borane → 5-Benzoyloxy-4-[4-(3-chlorophenoxy)-3-hydroxy-1-butenyl]-hexahydro-2H-cyclopenta[b]furan-2-one

HRID 480214Notes

Reaction equation

HRID 480214 reaction equation
[C:1]([O:9][CH:10]1[CH2:18][CH:13]2[O:14][C:15](=[O:17])[CH2:16][CH:12]2[CH: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][CH:10]1[CH2:18][CH:13]2[O:14][C:15](=[O:17])[CH2:16][CH:12]2[CH:11]1[CH:19]=[CH:20][CH: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 9923113Chlorobis((1S,2R,3S,5S)-2,6,6-trimethylbicyclo(3.1.1)hept-3-yl)boraneHCID 739939355-benzoyloxy-4-[4-(3-chlorophenoxy)-3-oxo-1-butenyl]-hexahydro-2H-cyclopenta[b]furan-2-one

Product 1

HCID 739939345-Benzoyloxy-4-[4-(3-chlorophenoxy)-3-hydroxy-1-butenyl]-hexahydro-2H-cyclopenta[b]furan-2-oneYield 49%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To a solution of [3aR, 4R(1E), 5R, 6aS]-5-benzoyloxy-4-[4-(3-chlorophenoxy)-3-oxo-1-butenyl]-hexahydro-2H-cyclopenta[b]furan-2-one (1; for preparation, see published European Patent Application EP 639563 A2, which is incorporated herein by this reference) (1.02 g, 2.32 mmol) in THF (10 mL) at −23° C. (bath temperature) was added dropwise a solution of (+)-B-chlorodiisopinocampheylborane (available from Aldrich Chemical Co., Milwaukee, Wis.) (1.4 g, 4.4 mmol) in THF (10 mL). The mixture was then warmed to 0° C. (bath temperature) and was quenched after 90 min by the addition of methanol (10 mL). Saturated NH4Cl was added (35 mL), the mixture was extracted with ethyl acetate (3×40 mL), dried (MgSO4), filtered, concentrated, and chromatographed on a 30 cm tall×41 mm diameter silica gel column eluting with 1:1 ethyl acetate:hexane to afford 2 (502 mg, 49%) as well as a mixture of 2 and its epimeric alcohol (254 mg, 23%).

Workup

  1. customfor preparation
  2. customat −23° C.
  3. customwas quenched after 90 min by the addition of methanol (10 mL)
  4. additionSaturated NH4Cl was added (35 mL)
  5. extractionthe mixture was extracted with ethyl acetate (3×40 mL)
  6. dry with materialdried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customchromatographed on a 30 cm tall×41 mm diameter silica gel column
  10. washeluting with 1:1 ethyl acetate

Sources & evidence

ORD record
ord-88b4c4f6c49e4a0fa6dd806e12e475c3
Source dataset
uspto-grants-2003_11
Patent number
US06649653B1

Reaction notes

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