Dimethyl Sulfoxide → HCID 87687100, compound

HRID 1396264Notes

Reaction equation

HRID 1396264 reaction equation
CS(C)=O.C(Cl)(=O)C(Cl)=O.[CH2:11]([O:18][C@@H:19]1[C@@H:27]([CH2:28][OH:29])[O:26][C@H:25]2[C@H:21]([N:22]=[C:23]([N:30]([CH3:32])[CH3:31])[S:24]2)[C@H:20]1[O:33][CH2:34][C:35]1[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=1)[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:27]([CH:28]=[O:29])[O:26][C@H:25]2[C@H:21]([N:22]=[C:23]([N:30]([CH3:32])[CH3:31])[S:24]2)[C@H:20]1[O:33][CH2:34][C:35]1[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=1)[C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 69081709HCID 69081709, compound

Product 1

HCID 87687100HCID 87687100, compoundYield 82.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of DMSO (14.6 g, 187 mmol) in dichloromethane (300 mL) was treated with oxalyl dichloride (17.7 g, 140 mmol) at −78° C. for 1 hour, then a solution of ((3aR,5R,6S,7R,7aR)-6,7-bis(benzyloxy)-2-(dimethylamino)-5,6,7,7a-tetrahydro-3aH-pyrano[3,2-d]thiazol-5-yl)methanol (10 g, 23 mmol) in dichloromethane (30 mL) was added slowly. The resulted solution was kept for 4 hours at −20° C., followed by the addition of triethylamine (28.3 g, 280 mmol) at −78° C. After additional 1 hour at −50° C., the reaction was quenched by water (300 mL) and extracted with dichloromethane (2×200 mL). The organic layers combined, washed with brine (3×100 mL) and dried over anhydrous sodium sulfate. After filtration, the filtrates were concentrated under vacuum to give a residue, which was purified by a silica gel column, eluted with 20% ethyl acetate in dichloromethane to give compound 95 as a yellow syrup (8.1 g, 80%). (ES, m/z): [M+H]+ 426.7; 1H NMR (300 MHz, CDCl3) δ 9.62 (s, 1H), 7.28-7.39 (m, 10H), 6.27-6.34 (m, 1H), 4.41-4.84 (m, 6H), 4.10-4.17 (m, 1H), 3.86-3.94 (m, 1H), 3.02 (s, 6H).

Workup

  1. waitAfter additional 1 hour at −50° C.
  2. customthe reaction was quenched by water (300 mL)
  3. extractionextracted with dichloromethane (2×200 mL)
  4. washwashed with brine (3×100 mL)
  5. dry with materialdried over anhydrous sodium sulfate
  6. filtrationAfter filtration
  7. concentrationthe filtrates were concentrated under vacuum
  8. customto give a residue, which
  9. customwas purified by a silica gel column
  10. washeluted with 20% ethyl acetate in dichloromethane

Sources & evidence

ORD record
ord-443310c53cb140cbb6a66f6299800341
Source dataset
uspto-grants-2014_12
Patent number
US08901087B2

Reaction notes

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