Dimethyl Sulfoxide → HCID 46862669, compound

HRID 1049955Notes

Reaction equation

HRID 1049955 reaction equation
C(Cl)(=O)C(Cl)=O.CS(C)=O.[CH2:11]([O:18][C@@H:19]1[CH2:23][C@H:22]([OH:24])[C@H:21]([CH2:25]/[CH:26]=[CH:27]\[CH2:28][CH2:29][CH2:30][C:31]([O:33][CH2:34][C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)=[O:32])[C@H:20]1[CH2:41][OH:42])[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[CH2:23][C:22](=[O:24])[C@H:21]([CH2:25]/[CH:26]=[CH:27]\[CH2:28][CH2:29][CH2:30][C:31]([O:33][CH2:34][C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)=[O:32])[C@H:20]1[CH:41]=[O:42])[C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 66786169HCID 66786169, compound

Product 1

HCID 46862669HCID 46862669, compoundYield 98.9%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a solution of oxalyl chloride (68.4 mmoL) in dichloromethane (10 volumes) at −78° C. was added DMSO (114.0 mmoL). The solution was stirred at −78° C. for 30-60 minutes followed by drop-wise addition of (5Z)-benzyl 7-[(1R,2S,3R,5S)-3-benzyloxy-5-hydroxy-2-(hydroxymethyl)cyclopentyl]hept-5-enoate (16, R1 is phenyl, R2 and R3 are H and R7 is benzyl, 10 g, 22.8 mmoL) in dichloromethane (10 volumes). The reaction mixture was stirred at −78° C. for 30 minutes at which time triethylamine (105.9 mmoL) was charged. The mixture was stirred at −78 to −60° C. for 4-6 hours followed by quenching with saturated aqueous ammonium chloride (10 volumes). The mixture was warmed to 0° C. The layers were separated; the organic layer was washed with saturated aqueous sodium carbonate, dried over sodium sulfate, filtered through Celite® and concentrated to dryness. The residue was purified by column chromatography (50% ethyl acetate in heptanes) to yield (5Z)-benzyl 7-[(1R,2R,3R)-3-benzyloxy-2-formyl-5-oxocyclopentyl]hept-5-enoate (17, R1 is phenyl, R2 and R3 are H and R7 is benzyl) as an oil (9.8 g).

Workup

  1. additionwas charged
  2. stirringThe mixture was stirred at −78 to −60° C. for 4-6 hours
  3. customby quenching with saturated aqueous ammonium chloride (10 volumes)
  4. temperatureThe mixture was warmed to 0° C
  5. customThe layers were separated
  6. washthe organic layer was washed with saturated aqueous sodium carbonate
  7. dry with materialdried over sodium sulfate
  8. filtrationfiltered through Celite®
  9. concentrationconcentrated to dryness
  10. customThe residue was purified by column chromatography (50% ethyl acetate in heptanes)

Sources & evidence

ORD record
ord-431c1a0c29f944538b052e7d212d0239
Source dataset
uspto-grants-2016_07
Patent number
US09382272B2

Reaction notes

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