Toluene-p-sulphonic anhydride → HCID 131736532, compound

HRID 1478931Notes

Reaction equation

HRID 1478931 reaction equation
C(C1N=[C:9]([C:11](C)(C)C)[CH:8]=[C:7]([C:15]([CH3:18])([CH3:17])C)N=1)(C)(C)C.C[Si](C)(C)N[Si](C)(C)C.[K].C1(C)C=CC(S([O:38][S:39]([C:42]2[CH:47]=[CH:46][C:45]([CH3:48])=[CH:44][CH:43]=2)(=[O:41])=[O:40])(=O)=O)=CC=1.S([C:54]1[CH:60]=[CH:59][C:57]([CH3:58])=[CH:56][CH:55]=1)([O-])(=O)=O.[O:61]1[C@H:68]([CH2:69][OH:70])[C@@H:66]([OH:67])[C@H:64]([OH:65])[CH:63]=[CH:62]1>>[CH2:58]([O:65][C@H:64]1[C@H:66]([O:67][CH2:17][C:15]2[CH:18]=[CH:11][CH:9]=[CH:8][CH:7]=2)[C@@H:68]([CH2:69][O:70][CH2:18][C:15]2[CH:7]=[CH:8][CH:9]=[CH:11][CH:17]=2)[O:61][C@H:62]([O:38][S:39]([C:42]2[CH:43]=[CH:44][C:45]([CH3:48])=[CH:46][CH:47]=2)(=[O:40])=[O:41])[CH2:63]1)[C:57]1[CH:59]=[CH:60][CH:54]=[CH:55][CH:56]=1

Participants

6

Reactant 5

HCID 77773Toluene-p-sulphonic anhydrideHCID 85570p-ToluenesulfonateHCID 2734736D-(+)-Glucal2×HCID 34401372,4,6-Tri-tert-butylpyrimidineHCID 45051783Silanamine, 1,1,1-trimethyl-N-(trimethylsilyl)-, potassium salt

Product 1

HCID 131736532HCID 131736532, compound

Conditions

Temperature
-78 °C

Procedure

A solution of donor 1a (21.7 mg, 0.050 mmol, 1.0 equiv.) and 2,4,6-tri-tert-butylpyrimidine (TTBP, 13.0 mg, 0.050 mmol, 1.0 equiv.) in 0.50 mL THF-d8 was cooled to −78° C. in a dry ice/acetone bath and treated dropwise with potassium hexamethyldisilazane (1 M in THF, 50.0 μL, 0.050 mmol, 1.0 equiv.). After 15 minutes, a solution of p-toluenesulfonic anhydride (17.1 mg, 0.053 mmol, 1.05 equiv.) in 0.50 mL THF-d8 was added rapidly to the reaction. The reaction was maintained at −78° C. for 30 min, transferred by syringe to a pre-cooled 5 mm Low Pressure/Vacuum Valve NMR tube, and promptly inserted into the NMR instrument probe pre-cooled to −78° C. for 1H NMR, 13C NMR, and 2D-Gradient HSQC data acquisition. The temperature was maintained for 2 hours, then warmed by 10 degrees every 10 minutes. At each 10 minute interval, the 1H NMR spectrum was recorded. At −78° C., a single compound was present in the spectrum. At −5° C., the spectrum began to show trace elimination of the tosylate to the corresponding glucal. Significant glucal was present at 25-78° C.

Workup

  1. customtransferred by syringe to a pre-cooled 5 mm Low Pressure/Vacuum Valve NMR tube
  2. temperaturepre-cooled to −78° C. for 1H NMR, 13C NMR, and 2D-Gradient HSQC data acquisition
  3. temperatureThe temperature was maintained for 2 hours
  4. temperaturewarmed by 10 degrees every 10 minutes
  5. waitAt each 10 minute interval
  6. customAt −78° C.
  7. customAt −5° C.
  8. customwas present at 25-78° C.

Sources & evidence

ORD record
ord-ad1de3644f0a48bbb2dc6371d0d37316
Source dataset
uspto-grants-2016_08
Patent number
US09403862B2

Reaction notes

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