(2R,4R,5R)-5-((Benzoyloxy)methyl)-3-oxotetrahydrofuran-2,4-diyl dibenzoate → (2R,3R,4R,5R)-2,4-dibenzoyloxy-5-benzoyloxymethyl-3-ethynyl-tetrahydrofuran-3-ol

HRID 2059568Notes

Reaction equation

HRID 2059568 reaction equation
[C:1]([Mg]Br)#[CH:2].[C:5]([O:13][C@@H:14]1[C:18](=[O:19])[C@H:17]([O:20][C:21](=[O:28])[C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[C@@H:16]([CH2:29][O:30][C:31](=[O:38])[C:32]2[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=2)[O:15]1)(=[O:12])[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1>C1COCC1>[C:5]([O:13][C@@H:14]1[C@:18]([C:1]#[CH:2])([OH:19])[C@H:17]([O:20][C:21](=[O:28])[C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[C@@H:16]([CH2:29][O:30][C:31](=[O:38])[C:32]2[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=2)[O:15]1)(=[O:12])[C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1

Participants

4

Reactant 2

HCID 10072943(2R,4R,5R)-5-((Benzoyloxy)methyl)-3-oxotetrahydrofuran-2,4-diyl dibenzoateHCID 178418486HCID 178418486, compound

Product 1

HCID 86642243(2R,3R,4R,5R)-2,4-dibenzoyloxy-5-benzoyloxymethyl-3-ethynyl-tetrahydrofuran-3-ol

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-50 °C

Procedure

A dry three-necked flask under N2 is charged with CeCl3 (23.6 g, 95.48 mmol, 4.4 equiv.) and THF (100 ml), which is cooled to −50° C. 1M Ethynylmagnesium bromide (186.8 ml, 93.4 mmol, 4.3 equiv.) is added over 20 min. The suspension is stirred at −50° C. for 1.5 hour. A solution of (2R,4R,5R)-2,4-dibenzoyloxy-5-benzoyloxymethyl-dihydrofuran-3-one (10.0 g, 21.7 mmol, 1.0 equiv.) in THF (80 ml) is added over 10 minutes. After addition, the suspension is stirred at −50° C. for 4 hour. The reaction is quenched with saturated NH4Cl (200 ml). After being allowed to warm to ambient temperature, the reaction mixture is filtered and extracted with CH2Cl2 (200 ml×3). The organic phase is dried over anhydrous Na2SO4, and concentrated to give a foam (2R, 3R,4R,5R)-2,4-dibenzoyloxy-5-benzoyloxymethyl-3-ethynyl-tetrahydrofuran-3-ol. 1H-NMR (400 MHz, CDCl3): δ 8.05-8.01 (m, 6H), 7.65-7.37 (m, 9H), 6.59 (s, 1H), 5.53 (d, 1H, J=2.8 Hz), 4.80-4.77 (m, 1H), 4.70 (dd, 1H, J=5.2 Hz, 12 Hz), 4.65 (dd, 1H, J=6 Hz, 12 Hz), 3.02 (bs, 1H), 2.65 (s, 1H).

Workup

  1. additionAfter addition
  2. stirringthe suspension is stirred at −50° C. for 4 hour
  3. customThe reaction is quenched with saturated NH4Cl (200 ml)
  4. temperatureto warm to ambient temperature
  5. filtrationthe reaction mixture is filtered
  6. extractionextracted with CH2Cl2 (200 ml×3)
  7. dry with materialThe organic phase is dried over anhydrous Na2SO4
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-37bdaecf09a3469fb561590d7390f573
Source dataset
uspto-grants-2012_10
Patent number
US08278282B2

Reaction notes

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