Ethyl Acetate → HCID 57752559, compound

HRID 227188Notes

Reaction equation

HRID 227188 reaction equation
[CH2:1]([O:8][C:9]1[C:25]([O:26][CH3:27])=[CH:24][C:12]([C:13]([N:15]2[CH2:19][C@H:18]([OH:20])[CH2:17][C@H:16]2[C:21]([O-])=[O:22])=[O:14])=[C:11]([N+:28]([O-:30])=[O:29])[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Li+].[BH4-].CCOC(C)=O>C1COCC1>[CH2:1]([O:8][C:9]1[C:25]([O:26][CH3:27])=[CH:24][C:12]([C:13]([N:15]2[CH2:19][C@H:18]([OH:20])[CH2:17][C@H:16]2[CH2:21][OH:22])=[O:14])=[C:11]([N+:28]([O-:30])=[O:29])[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 8857Ethyl AcetateHCID 4148881Lithium borohydrideHCID 86614428HCID 86614428, compound

Product 1

HCID 57752559HCID 57752559, compoundYield 90.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

A solution of the ester 19 (3.8 g, 8.83 mmol, 1.0 equiv.) in THF (100 mL) was cooled to 0° C. and treated with LiBH4 (0.29 g, 13.25 mmol, 1.5 equiv.) in portions. After stirring for 30 min at 0° C., the reaction mixture was allowed to warm to room temperature and stirred under a nitrogen atmosphere for 4 h at which time TLC (SiO2, EtOAc) revealed complete consumption of ester 19. The mixture was cooled to 0° C. again and water (100 mL) was carefully added followed by 1N HCl (250 mL) which provoked vigorous effervescence. After evaporation of the THF in vacuo, the mixture was neutralised to pH 7 with 1N NaOH. The aqueous solution was then extracted with EtOAc (4×70 mL), the combined organic layers washed with brine (50 mL), dried (MgSO4), filtered and evaporated in vacuo to furnished the pure diol 20 (3.2 g, 7.96 mmol, 90%), which was used in the subsequent reaction without further purification. [α]29D=−96° (c=0.15, CHCl3); 1H NMR (CDCl3, 400 MHz): δ 1.85-1.99 (m, 1H, 1-H), 2.09-2.28 (m, 1H, 1-H), 3.11-3.20 (m, 1H, 11-H), 3.25-3.39 (m, 1H, 11-H), 3.70-3.82 (m, 1H, 3-H), 3.85-4.04 (m, 5H, 3-H, 7-OMe, OH), 4.30-4.38 (m, 1H, 11a-H), 4.46-4.61 (m, 2H, 2-H), 5.20 (m, 2H, OCH2Ph), 6.86 (s, 1H, 6-H), 7.29-7.50 (m, 5H, Ph), 7.74 (s, 1H, 9-H); 13C NMR (CDCl3, 100 MHz): δ 37.1, 56.8, 56.9, 59.9, 65.0, 69.4, 71.4, 109.1, 109.3, 127.6, 127.7, 128.5, 128.8, 135.2, 137.2, 148.2, 155; IR (neat): 3357, 2938, 1614, 1576, 1520, 1454, 1434, 1333, 1276, 1220, 1069, 1048, 1006, 730, 698, 647 cm−1; MS (ES+) m/z (relative intensity) 426 ([M+Na]+., 5), 403 ([M+H]+., 100), 404 ([M+2H]+., 40).

Workup

  1. temperatureto warm to room temperature
  2. customconsumption of ester 19
  3. temperatureThe mixture was cooled to 0° C. again
  4. additionwater (100 mL) was carefully added
  5. customAfter evaporation of the THF in vacuo
  6. extractionThe aqueous solution was then extracted with EtOAc (4×70 mL)
  7. washthe combined organic layers washed with brine (50 mL)
  8. dry with materialdried (MgSO4)
  9. filtrationfiltered
  10. customevaporated in vacuo

Sources & evidence

ORD record
ord-8aea5667e19d4bbab973bbe3dd5b71a7
Source dataset
uspto-grants-2009_07
Patent number
US07557099B2

Reaction notes

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