Dimethyl Sulfoxide → HCID 86685128, compound

HRID 1913018Notes

Reaction equation

HRID 1913018 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[CH2:11]([O:18][C@H:19]1[C@H:24]([O:25][CH2:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[C@@H:23]([O:33][CH2:34][C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)[C@@:22]([C:43]2[CH:48]=[CH:47][C:46]([Cl:49])=[C:45]([CH2:50][C:51]3[CH:56]=[CH:55][C:54]([O:57][CH2:58][CH3:59])=[C:53]([F:60])[CH:52]=3)[CH:44]=2)([O:41][CH3:42])[O:21][C@@H:20]1[CH2:61][OH:62])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.C(N(CC)CC)C>ClCCl>[CH2:11]([O:18][C@H:19]1[C@H:24]([O:25][CH2:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)[C@@H:23]([O:33][CH2:34][C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)[C@@:22]([C:43]2[CH:48]=[CH:47][C:46]([Cl:49])=[C:45]([CH2:50][C:51]3[CH:56]=[CH:55][C:54]([O:57][CH2:58][CH3:59])=[C:53]([F:60])[CH:52]=3)[CH:44]=2)([O:41][CH3:42])[O:21][C@@H:20]1[CH:61]=[O:62])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 68015197HCID 68015197, compound

Product 1

HCID 86685128HCID 86685128, compoundYield 100%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Conditions

Temperature
-78 °C

Procedure

Oxalyl chloride (1.17 mL, 13.6 mmol) was dissolved in 20 mL dichloromethane and cooled to −78° C., followed by dropwise addition of a solution (20 mL) of dimethyl sulfoxide (1.56 mL, 21.9 mmol) in dichloromethane and a solution (50 mL) of [(2R,3R,4S,5R,6S)-3,4,5-tribenzyloxy-6-[4-chloro-3-[(4-ethoxy-3-fluoro-phenyl)methyl]phenyl]-6-methoxy-tetrahydropyran-2-yl]methanol 4i (7.6 g, 10.45 mmol) in dichloromethane. The reaction mixture was stirred for 30 minutes at −78° C. Triethylamine (7.25 mL, 52.3 mmol) was added before the reaction mixture was warmed and stirred for 2 hours at room temperature. Thereafter, the reaction mixture was partitioned after 50 mL 1 M hydrochloric acid were added. The organic extract was washed with saturated sodium chloride solution (50 mL×2). The aqueous phase was extracted with dichloromethane (50 mL). The organic extract was combined, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure to obtain the title compound (2S,3S,4S,5R,6S)-3,4,5-tribenzyloxy-6-[4-chloro-3-[(4-ethoxy-3-fluoro-phenyl)methyl]phenyl]-6-methoxy-tetrahydropyran-2-carbaldehyde 4j (7.58 g, colourless grease), which was used directly without purification in the next step.

Workup

  1. temperaturewas warmed
  2. stirringstirred for 2 hours at room temperature
  3. customThereafter, the reaction mixture was partitioned after 50 mL 1 M hydrochloric acid
  4. additionwere added
  5. extractionThe organic extract
  6. washwas washed with saturated sodium chloride solution (50 mL×2)
  7. extractionThe aqueous phase was extracted with dichloromethane (50 mL)
  8. extractionThe organic extract
  9. dry with materialdried over anhydrous magnesium sulfate
  10. filtrationfiltered
  11. concentrationThe filtrate was concentrated under reduced pressure

Sources & evidence

ORD record
ord-0e995974e7e149e3bb78b52c3d9ef670
Source dataset
uspto-grants-2013_12
Patent number
US08609622B2

Reaction notes

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