Pyridine → HCID 90357162, compound

HRID 522180Notes

Reaction equation

HRID 522180 reaction equation
[CH2:1]([O:8][C@H:9]1[C@@H:14]([O:15][CH2:16][C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[C@H:13]([O:23][CH2:24][C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=2)[C@@H:12]([CH2:31][O:32][CH2:33][C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)[O:11][C@@H:10]1[CH2:40][P:41](=[O:44])([O-:43])[O-:42])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.N1C=CC=CC=1.C[Si](Br)(C)C>C(#N)C>[CH2:1]([O:8][C@H:9]1[C@@H:14]([O:15][CH2:16][C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=2)[C@H:13]([O:23][CH2:24][C:25]2[CH:26]=[CH:27][CH:28]=[CH:29][CH:30]=2)[C@@H:12]([CH2:31][O:32][CH2:33][C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)[O:11][C@@H:10]1[CH2:40][P:41](=[O:42])([OH:43])[OH:44])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 1049PyridineHCID 76113BromotrimethylsilaneHCID 131735508HCID 131735508, compound

Product 1

HCID 90357162HCID 90357162, compoundYield 90.8%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Procedure

To a solution of (((2S,3S,4S,5R,6R)-3,4,5-tris(benzyloxy)-6-((benzyloxy)methyl)tetrahydro-2H-pyran-2-yl)methyl)phosphonate (0.6 g, 0.89 mmol, 1.0 equiv) in dry acetonitrile (60 mL) was added pyridine (1.1 mL, 10.2 mmol, 11.5 equiv) at 0° C. under argon atmosphere. TMSBr (2.5 mL, 17.7 mmol, 20 equiv) dissolved in dry acetonitrile (25 mL) was added dropwise to the reaction mixture at 0° C. which was stirred for 10 minutes and then warmed to room temperature and stirred for 3 hours. The volatiles were removed in vacuo (bath temperature <15° C.) to give an oil. Ice cold water (20 mL) was added, and the organic material was extracted into DCM (2×80 mL). The combined organic layers were dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo (bath temp <15° C.) to give ((((2S,3S,4S,5R,6R)-3,4,5-tris(benzyloxy)-6-((benzyloxy)methyl)tetrahydro-2H-pyran-2-yl)methyl)phosphonic acid as a pale green solid (0.50 g). The material thus obtained was used without further purification. ESI (M+1) m/z: 619.0; calc for C35H39O8P 618.2.

Workup

  1. additionwas added dropwise to the reaction mixture at 0° C. which
  2. stirringstirred for 3 hours
  3. customThe volatiles were removed in vacuo (bath temperature <15° C.)
  4. customto give an oil
  5. extractionthe organic material was extracted into DCM (2×80 mL)
  6. dry with materialThe combined organic layers were dried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo (bath temp <15° C.)

Sources & evidence

ORD record
ord-f933f6dd4085426091cb478ee1bebd2a
Source dataset
uspto-grants-2016_05
Patent number
US09328134B2

Reaction notes

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