Dimethyl Sulfoxide → HCID 86685122, compound

HRID 1913005Notes

Reaction equation

HRID 1913005 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])[C:52]=3[F:61])[CH:44]=2)([O:41][CH3:42])[O:21][C@@H:20]1[CH2:62][OH:63])[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:36]=[CH:37][CH:38]=[CH:39][CH:40]=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])[C:52]=3[F:61])[CH:44]=2)([O:41][CH3:42])[O:21][C@@H:20]1[CH:62]=[O:63])[C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 86685120HCID 86685120, compound

Product 1

HCID 86685122HCID 86685122, compoundYield 96.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Conditions

Temperature
-78 °C

Procedure

Oxalyl chloride (0.37 mL, 4.37 mmol) was dissolved in 20 mL dichloromethane and cooled to −78° C., followed by dropwise addition of a solution (10 mL) of dimethyl sulfoxide (0.5 mL, 7.05 mmol) in dichloromethane and a solution (20 mL) of [(2R,3R,4S,5R,6S)-3,4,5-tribenzyloxy-6-[4-chloro-3-[(4-ethoxy-2,3-difluoro-phenyl)methyl]phenyl]-6-methoxy-tetrahydropyran-2-yl]methanol 3i (2.5 g, 3.36 mmol) in dichloromethane in turn. The reaction mixture was stirred for 30 minutes at −78° C. Triethylamine (2.33 mL, 16.8 mmol) was added before the reaction mixture was warmed and stirred for 16 hours at room temperature. Thereafter, the reaction mixture was partitioned after 15 mL 1 M hydrochloric acid were added. The organic extract was washed with saturated sodium chloride solution (20 mL×2) and 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-2,3-difluoro-phenyl)methyl]phenyl]-6-methoxy-tetrahydropyran-2-carbaldehyde 3j (2.4 g, yellow grease), yield: 96.0%.

Workup

  1. temperaturewas warmed
  2. stirringstirred for 16 hours at room temperature
  3. customThereafter, the reaction mixture was partitioned after 15 mL 1 M hydrochloric acid
  4. additionwere added
  5. extractionThe organic extract
  6. washwas washed with saturated sodium chloride solution (20 mL×2)
  7. dry with materialdried over anhydrous magnesium sulfate
  8. filtrationfiltered
  9. concentrationThe filtrate was concentrated under reduced pressure

Sources & evidence

ORD record
ord-3c5b9f34a3da407a86cfb26a9cfc909e
Source dataset
uspto-grants-2013_12
Patent number
US08609622B2

Reaction notes

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