Pyridine → p-Methylphenyl 3,6-di-o-benzoyl-2-deoxy-2-(2,2,2-trichloroethoxylcarbonylamino)-1-thio-beta-d-glucopyranoside

HRID 1862754Notes

Reaction equation

HRID 1862754 reaction equation
[C:1]([O:4][C@H:5]1[C@H:18]([O:19]C(=O)C)[C@@H:17]([CH2:23][O:24][C:25](=[O:27])[CH3:26])[O:16][C@@H:7]([S:8][C:9]2[CH:14]=[CH:13][C:12]([CH3:15])=[CH:11][CH:10]=2)[C@@H:6]1[NH:28][C:29]([O:31][CH2:32][C:33]([Cl:36])([Cl:35])[Cl:34])=[O:30])(=[O:3])[CH3:2].C[O-].[Na+].N1[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=1.C(Cl)([C:48]1[CH:53]=[CH:52]C=[CH:50][CH:49]=1)=O>CO.CN(C1C=CN=CC=1)C.C(Cl)Cl>[C:1]([O:4][C@H:5]1[C@H:18]([OH:19])[C@@H:17]([CH2:23][O:24][C:25](=[O:27])[C:26]2[CH:52]=[CH:53][CH:48]=[CH:49][CH:50]=2)[O:16][C@@H:7]([S:8][C:9]2[CH:10]=[CH:11][C:12]([CH3:15])=[CH:13][CH:14]=2)[C@@H:6]1[NH:28][C:29]([O:31][CH2:32][C:33]([Cl:36])([Cl:35])[Cl:34])=[O:30])(=[O:3])[C:2]1[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=1

Participants

8

Reactant 4

HCID 1049PyridineHCID 7412Benzoyl chlorideHCID 10942334Sodium MethoxideHCID 15497894p-Methylphenyl 3,4,6-Tri-O-acetyl-2-deoxy-2(2,2,2-trichloroethoxylcarbonylamino)-1-thio-beta-D-glucopyranoside

Product 1

HCID 11216026p-Methylphenyl 3,6-di-o-benzoyl-2-deoxy-2-(2,2,2-trichloroethoxylcarbonylamino)-1-thio-beta-d-glucopyranosideYield 56%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 887MethanolSolventHCID 6344DichloromethaneSolvent

Procedure

Compound 21 (2.0 g, 3.41 mmol) in MeOH (10 mL) was treated with a catalytic amount of 1M NaOMe for 5 h, then neutralized with IR-120 (H+), filtered and concentrated. To a solution of the crude product (610 mg, 1.324 mmol), pyridine (700 μL) and DMAP (50 mg) in CH2Cl2 (20 mL), was added BzCl (338 μL, 2.916 mmol). The mixture was refluxed for 5 h under Ar, then concentrated and coevaporated twice with toluene, diluted with CH2Cl2 (100 mL), washed with 10% aq. H2SO4, brine, and sat. aq NaHCO3, dried over Na2SO4, filtered and concentrated. Column chromatography (Hexane/AcOEt, 2:1 to 1:2) of the residue gave 27 (495 mg, 56%) as white white solid; [α]D22 +28.4° (c, 0.5, CHCl3); 1H-NMR (500 MHz, CDCl3), δ 5.50 (d, 1H, J=9.5 Hz, H-2), 5.41 (t, 1H, J=9.5 Hz, H-3), 4.844 (d, 1H, J=10.0 Hz, H-1), 4.74-4.64 (m, 3H), 4.55 (d, 1H, J=12.0 Hz, OCH2CCl3), 3.90 (q, 1H, J=10.0 Hz, H-2), 3.79 (m, 2H, H-5, H-4), 3.42 (d, 1H, J=5.0 Hz, OH), 2.27 (s, 3H, Me); HRMS (M+Cs) calcd for C30H28O8Cl3NSCs 799.9655, found 799.9680.

Workup

  1. filtrationfiltered
  2. concentrationconcentrated
  3. temperatureThe mixture was refluxed for 5 h under Ar
  4. concentrationconcentrated
  5. additiondiluted with CH2Cl2 (100 mL)
  6. washwashed with 10% aq. H2SO4, brine, and sat. aq NaHCO3
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-905f7c467c0a4a759e2016542f308939
Source dataset
uspto-grants-2003_03
Patent number
US06538117B1

Reaction notes

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