Trifluoromethanesulfonic anhydride → HCID 131715978, compound

HRID 1905100Notes

Reaction equation

HRID 1905100 reaction equation
N12CCCCC1C=NCCC2.FC(F)(F)S(OS(C(F)(F)F)(=O)=O)(=O)=O.[CH2:27]([O:30][C:31]([C@@H:33]1[C:39](=O)[CH2:38][C@H:37]2[N:34]1[C:35](=[O:51])[C@H:36]2[C@H:41]([C:47]([CH3:50])([CH3:49])[CH3:48])[CH2:42][O:43][SiH:44]([CH3:46])[CH3:45])=[O:32])[CH:28]=[CH2:29].C(N(C(C)C)C(C)C)C.[SH:61][C:62]1[CH:67]=[CH:66][N:65]=[CH:64][CH:63]=1.C([O-])(O)=O.[Na+]>C1COCC1.C(OCC)(=O)C.CN(C=O)C>[N:65]1[CH:66]=[CH:67][C:62]([S:61][C:39]2[CH2:38][C@@H:37]3[C@H:36]([C@H:41]([C:47]([CH3:50])([CH3:48])[CH3:49])[CH2:42][O:43][SiH:44]([CH3:46])[CH3:45])[C:35](=[O:51])[N:34]3[C:33]=2[C:31]([O:30][CH2:27][CH:28]=[CH2:29])=[O:32])=[CH:63][CH:64]=1

Participants

10

Reactant 6

HCID 67749Trifluoromethanesulfonic anhydrideHCID 81531DiisopropylethylamineHCID 3141121,5-Diazabicyclo(5,4,0)undec-5-eneHCID 516892Sodium BicarbonateHCID 131715977HCID 131715977, compoundHCID 178418431pyridine-4-thiol

Product 1

HCID 131715978HCID 131715978, compoundYield 67.3%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

Procedure

1.94 ml (13 mmol) of 1,5-diazabicyclo[5.4.0]undec-5-ene (DBU) and, after 20 minutes, 2.2 ml (13 mmol) of trifluoromethanesulphonic anhydride were added dropwise to a solution, which had been cooled to -78° C., of 3.68 g (10 mmol) of (2S,5R,6S)-2-allyloxycarbonyl-3,7-dioxo-6-[(1R)-1-tert.-butyldimethylsilyloxyethyl]-1-azabicyclo[3.2.0]heptane in 100 ml of anhydrous THF. The mixture was then stirred at -78° C. for 30 minutes and the solution was concentrated in vacuo to about 40 ml without the temperature rising above -20° C. Then, successively 20 ml of DMF, 2.1 ml (12 mmol) of ethyl diisopropylamine and 1.33 g (12 mmol) of 4-mercaptopyridine were added and the mixture was stirred at -20° C. for 1 h. The mixture was then diluted with ethyl acetate and poured into cold, saturated NaHCO3 solution. Extraction was carried out with ethyl acetate, followed by washing with saturated NaCl solution and drying with MgSO4. After evaporation of the solvent in vacuo and chromatography of the residue on 600 g of silica gel (toluene:ethyl acetate), 3.1 g (66%) of the title compound were obtained as a viscous oil, Rf: 0.30 (toluene:ethyl acetate 7:3).

Workup

  1. concentrationthe solution was concentrated in vacuo to about 40 ml without the temperature
  2. customrising above -20° C
  3. stirringthe mixture was stirred at -20° C. for 1 h
  4. extractionExtraction
  5. washby washing with saturated NaCl solution
  6. dry with materialdrying with MgSO4
  7. customAfter evaporation of the solvent in vacuo and chromatography of the residue on 600 g of silica gel (toluene:ethyl acetate)

Sources & evidence

ORD record
ord-f486ea1d1c1a4317b283f5e4ffb69e6e
Source dataset
uspto-grants-1989_06
Patent number
US04841042

Reaction notes

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