HCID 131725689, compound → HCID 91390783, compound

HRID 1795071Notes

Reaction equation

HRID 1795071 reaction equation
[N:1]([C@@H:4]([CH:12]1[CH2:17][CH2:16][CH:15]([CH2:18][O:19][Si](C(C)C)(C(C)C)C(C)C)[CH2:14][CH2:13]1)[C:5]([N:7]1[CH2:11][CH2:10][S:9][CH2:8]1)=[O:6])=[N+:2]=[N-:3]>O.C(#N)C>[N:1]([C@@H:4]([CH:12]1[CH2:17][CH2:16][CH:15]([CH2:18][OH:19])[CH2:14][CH2:13]1)[C:5](=[O:6])[N:7]1[CH2:11][CH2:10][S:9][CH2:8]1)=[N+:2]=[N-:3]

Participants

4

Reactant 1

HCID 131725689HCID 131725689, compound

Product 1

HCID 91390783HCID 91390783, compoundYield 94.6%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6342AcetonitrileSolvent

Procedure

3-[(2S)-2-Azido-2-(4-{[(triisopropylsilyl)oxy]methyl}cyclohexyl)-ethanoyl]-1,3-thiazolidine (isomer II, 130 mg, 0.29 mmol) from Example 6, Step I was dissolved in 3 mL of 15% HF (45% in H2O) in acetonitrile and stirred for 2 h. The solvent was removed and the residue was dissolved in ethyl acetate and then neutralized with aqueous sodium bicarbonate. The organics were separated, dried (Na2SO4) and filtered. Evaporation of the solvent afforded 78 mg of {4-[(1S)-1-azido-2-oxo-2-(1,3-thiazolidin-3-yl)ethyl]cyclohexyl}methanol. A portion of this material (24 mg, 0.084 mmol) was dissolved in wet THF and triphenyl phosphine (26 mg, 0.1 mmol) was added to the solution. The mixture was heated in an oil bath at 60° C. for 5 h, cooled, concentrated and purified by preparative TLC on silica gel (eluent: 5 to 10% methanol in CH2Cl2) to give the title compound. 1H NMR (500 MHz, CD3OD, HCl salt) δ 4.71 (dd, 1H, J=3 and 6 Hz), 4.58 (d, 0.45H, J=9.2 Hz), 4.48 (d, 0.55H, J=9.2 Hz), 4.18 (d, 0.45H, J=5.9 Hz), 4.11 (d, 0.55H, J=5.9 Hz), 3.93 (m, 0.55H), 3.88 (m, 0.45H), 3.88 (m, 0.45H), 3.79 (m, 1H), 3.17 (m, 1H), 3.36 (d, 2H, J=6.1 Hz), 3.09 (m, 1H), 1.98–1.78 (m, 4H), 1.40 (m, 1H), 1.26 (m, 1H), 1.11(m, 1H), 1.01 (m, 2H). 3-[(2S)-2-Azido-2-(4-{[(triisopropylsilyl)oxy]methyl}cyclohexyl)-ethanoyl]-1,3-thiazolidine (isomer I, 78 mg) was converted to the title compound in a manner identical to that described for isomer II. 1H NMR (500 MHz, CD3OD, HCl salt) δ 4.71 (dd, 1H, J=8 and 10 Hz), 4.58 (dd, 0.45H, J=2 and 9 Hz), 4.48 (d, 0.55H, J=2 and 9 Hz), 4.20 (d, 0.45H, J=6.2 Hz), 4.12 (d, 0.55H, J=6.2 Hz), 3.96 (m, 0.55H), 3.88 (m, 0.45H), 3.88 (m, 0.45H), 3.79 (m, 1H), 3.55 (d, 2H, J=5.9 Hz), 3.14 (m, 1H), 3.09 (m, 1H), 1.98 (m, 1H), 1.80 (m, 3H), 1.58 (m, 3H), 1.39 (m, 2H).

Workup

  1. customThe solvent was removed
  2. dissolutionthe residue was dissolved in ethyl acetate
  3. customThe organics were separated
  4. dry with materialdried (Na2SO4)
  5. filtrationfiltered
  6. customEvaporation of the solvent

Sources & evidence

ORD record
ord-9c53104fdd08449f8992c62de6075155
Source dataset
uspto-grants-2006_04
Patent number
US07026316B2

Reaction notes

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