Lithium tri-tert-butoxyaluminohydride → HCID 56605060, compound

HRID 1516250Notes

Reaction equation

HRID 1516250 reaction equation
[C:1]([O:9][CH2:10][C@@H:11]1[C@@H:15]([O:16][C:17](=[O:24])[C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[C@:14]([F:26])([CH3:25])[C:13](=[O:27])[O:12]1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[H-].C(O[Al](OC(C)(C)C)OC(C)(C)C)(C)(C)C.[Li+]>>[C:1]([O:9][CH2:10][C@@H:11]1[C@@H:15]([O:16][C:17](=[O:24])[C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=2)[C@:14]([F:26])([CH3:25])[CH:13]([OH:27])[O:12]1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

3

Reactant 2

HCID 16710494Lithium tri-tert-butoxyaluminohydrideHCID 42625091(2R)-2-Deoxy-2-fluoro-2-methyl-D-erythro-pentonic acid γ-lactone 3,5-dibenzoate

Product 1

HCID 56605060HCID 56605060, compoundYield 99.5%

Conditions

Temperature
0 °C

Procedure

To a stirred solution of ((2R,3R,4R)-3-benzoyloxy-4-fluoro-4-methyl-5-oxo-tetrahydrofuran-2-yl)methyl benzoate (about 60 g, 161 mmol) in tetrahydrafuran (about 300 ml) cooled to about −10° C., then lithium tri tertiary butoxy aluminum hydride (about 241.9 ml, 241 mmol) was added and stirred at about 0° C. for 1 hour. Completion of the reaction was monitored by thin layer chromatography, quenched with saturated ammonium chloride solution. Tetrahydrafuran was removed under reduced pressure and the aqueous layer was extracted with ethyl acetate. The combined organic extracts were washed with water, brine and dried over sodium sulphate. The organic layer was removed under reduced pressure and the residue was purified by silica gel column chromatography using 16% ethyl acetate: hexane as eluent furnished title compound (about 60 g) as a colorless liquid. Yield: 99.46%; 1H NMR (300 MHz, CDCl3): δ 8.11-8.00 (m, 4H), 7.61-7.37 (m, 6H), 5.65 (dd, 1H, J=23.4 Hz, 7.8 Hz, 7.5 Hz), 5.34 (dd, 1H, J=9.6 Hz, 2.7 Hz), 4.69-4.66 (m, 1H), 4.57-4.53 (m, 2H), 3.40 (brs, 1H, —OH), 1.60-1.56 (m, 3H, J=22.5); Mass: [M+Na]+: 397 (100%); IR cm−: 3439, 3070, 2940, 2868, 1733, 1729, 1453, 1274, 1115, 710.

Workup

  1. customquenched with saturated ammonium chloride solution
  2. customTetrahydrafuran was removed under reduced pressure
  3. extractionthe aqueous layer was extracted with ethyl acetate
  4. washThe combined organic extracts were washed with water, brine
  5. dry with materialdried over sodium sulphate
  6. customThe organic layer was removed under reduced pressure
  7. customthe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-3982f78ef6c64a9f8896f0a4f4cae037
Source dataset
uspto-grants-2012_07
Patent number
US08227431B2

Reaction notes

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