4-Toluenesulfonyl chloride → HCID 59153314, compound

HRID 1854257Notes

Reaction equation

HRID 1854257 reaction equation
O[CH2:2][C@H:3]1[O:11][C@H:10]2[C@H:6]([N:7]=[C:8]([CH2:12][CH2:13][CH3:14])[S:9]2)[C@@H:5]([OH:15])[C@@H:4]1[OH:16].S(Cl)(C1C=CC(C)=CC=1)(=O)=O.[N-:28]=[N+:29]=[N-:30].[Na+]>N1C=CC=CC=1.C(Cl)Cl>[N:28]([CH2:2][C@H:3]1[O:11][C@H:10]2[C@H:6]([N:7]=[C:8]([CH2:12][CH2:13][CH3:14])[S:9]2)[C@@H:5]([OH:15])[C@@H:4]1[OH:16])=[N+:29]=[N-:30]

Participants

6

Reactant 3

HCID 73974-Toluenesulfonyl chlorideHCID 33557Sodium AzideHCID 11507040HCID 11507040, compound

Product 1

HCID 59153314HCID 59153314, compoundYield 82%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 6344DichloromethaneSolvent3×

Procedure

(3aR,5R,6S,7R,7aR)-5-(hydroxymethyl)-2-propyl-5,6,7,7a-tetrahydro-3aH-pyrano[3,2-d]thiazole-6,7-diol (200 mg, 0.81 mmol) was dissolved in pyridine (2 mL) and CH2Cl2 (2 mL) and cooled to 0° C. Tosyl chloride (230 mg, 1.2 mmol) was then added and the solution allowed to warm to room temperature over 1 h. The mixture was diluted with CH2Cl2 (10 mL) and washed with water (2×5 mL), dried (MgSO4), filtered and concentrated. The resultant colourless residue (280 mg) was taken up in DMF (3 mL) and NaN3 (158 mg, 2.4 mmol) was added. The resultant mixture was stirred at 55° C. for 2 days. Concentration of the mixture gave a residue which was taken up in CH2Cl2 (20 mL) and washed with water (2×5 mL), dried (MgSO4), filtered and concentrated. Flash chromatography of the residue on silica gel (MeOH:EtOAc, 1:9) gave 180 mg (82% yield) of (3aR,5R,6S,7R,7aR)-5-(azidomethyl)-2-propyl-5,6,7,7a-tetrahydro-3aH-pyrano[3,2-d]thiazole-6,7-diol (50) as a colourless oil. 1H NMR (500 MHz, methanol-d4): δ 0.98 (t, 3H, J=7.3 Hz), 1.63-1.67 (m, 2H), 2.46-2.50 (m, 2H), 3.33 (m, 1H), 3.54 (dd, 1H, J=4.3, 9.5 Hz), 3.44 (dd, 1H, 2.3, 12.0 Hz), 3.55 (dd, 1H, J=6.2, 12.0 Hz), 4.06 (dd, 1H, J=4.4, 4.6 Hz), 4.29 (m, 1H, J=4.3 Hz), 6.31 (d, 1H, J=6.9 Hz).

Workup

  1. washwashed with water (2×5 mL)
  2. dry with materialdried (MgSO4)
  3. filtrationfiltered
  4. concentrationconcentrated
  5. customConcentration of the mixture gave a residue which
  6. washwashed with water (2×5 mL)
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-3f9066c67226407d8115b7221f1b7d61
Source dataset
uspto-grants-2015_02
Patent number
US08962664B2

Reaction notes

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