Dichloromethane → [(4R,6S)-6-methanesulfonyloxymethyl-2,2-dimethyl-[1,3]dioxan-4-yl]-acetic acid

HRID 445931

Reaction equation

HRID 445931 reaction equation
C([O:5][C:6](=[O:18])[CH2:7][C@H:8]1[CH2:13][C@@H:12]([CH2:14][OH:15])[O:11][C:10]([CH3:17])([CH3:16])[O:9]1)(C)(C)C.ClCCl.C(N(CC)CC)C.[CH3:29][S:30](Cl)(=[O:32])=[O:31]>O>[CH3:29][S:30]([O:15][CH2:14][C@H:12]1[O:11][C:10]([CH3:17])([CH3:16])[O:9][C@@H:8]([CH2:7][C:6]([OH:5])=[O:18])[CH2:13]1)(=[O:32])=[O:31]

Participants

6

Reactant 4

HCID 6344DichloromethaneHCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 9816650tert-Butyl 2,4-dideoxy-3,5-O-(1-methylethylidene)-D-erythro-hexonate

Product 1

HCID 22850992[(4R,6S)-6-methanesulfonyloxymethyl-2,2-dimethyl-[1,3]dioxan-4-yl]-acetic acidYield 92%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

tert-Butyl-2-[(4R,6S)-6-hydroxymethyl-2,2-dimethyl-[1,3]dioxan-4-yl]acetate (10.0 g) and dichloromethane (60.0 mL) were added to a reactor. The reaction mixture was cooled to 0˜5° C. Triethylamine (12.9 mL) and methanesulfonyl chloride (3.6 mL) was added to the reaction mixture, which was then stirred at 0˜5° C. for 1 hour. Water (500.0 mL) was added to the reaction mixture under stirring. The separated organic layer was concentrated under reduced pressure. Methanol (40.0 mL), water (20.0 mL), and sodium hydroxide (3.4 g) were added to the resulting residue. The reaction mixture was stirred at 40° C. for over 12 hours and then concentrated under reduced pressure. Water (30.0 mL) and ethyl acetate (60.0 mL) were added to the resulting residue and then the pH of the reaction mixture was adjusted to 2.0˜4.0 using 6N hydrochloric acid solution. The separated organic layer was concentrated under reduced pressure to obtain [(4R,6S)-6-methanesulfonyloxymethyl-2,2-dimethyl-[1,3]dioxan-4-yl]-acetic acid as a gel form (10.0 g, yield 92%).

Workup

  1. temperatureThe reaction mixture was cooled to 0˜5° C
  2. stirringunder stirring
  3. concentrationThe separated organic layer was concentrated under reduced pressure
  4. additionMethanol (40.0 mL), water (20.0 mL), and sodium hydroxide (3.4 g) were added to the resulting residue
  5. stirringThe reaction mixture was stirred at 40° C. for over 12 hours
  6. concentrationconcentrated under reduced pressure
  7. additionWater (30.0 mL) and ethyl acetate (60.0 mL) were added to the resulting residue
  8. concentrationThe separated organic layer was concentrated under reduced pressure

Sources & evidence

ORD record
ord-330b3adbeef84ccdb44501e01b286603
Source dataset
uspto-grants-2013_07
Patent number
US08476432B2

Linked notes

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