Acetic Acid → HCID 11503270, compound

HRID 558023Notes

Reaction equation

HRID 558023 reaction equation
[C:1]([O:4][C@H:5]1[C@H:13]([O:14][C:15](=[O:17])[CH3:16])[C@@H:12]([CH2:18][O:19]C(=O)C)[O:11][C@H:7]([S:8][CH2:9][CH3:10])[C@H:6]1[N:23]=[N+:24]=[N-:25])(=[O:3])[CH3:2].CC(O)=O.[Si:30](Cl)([C:33]([CH3:36])([CH3:35])[CH3:34])([CH3:32])[CH3:31]>CO>[C:1]([O:4][C@H:5]1[C@H:13]([O:14][C:15](=[O:17])[CH3:16])[C@@H:12]([CH2:18][O:19][Si:30]([C:33]([CH3:36])([CH3:35])[CH3:34])([CH3:32])[CH3:31])[O:11][C@H:7]([S:8][CH2:9][CH3:10])[C@H:6]1[N:23]=[N+:24]=[N-:25])(=[O:3])[CH3:2]

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 28928tert-Butyldimethylsilyl chlorideHCID 90858637HCID 90858637, compound

Product 1

HCID 11503270HCID 11503270, compoundYield 99%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

To a solution of 22 (3.71 g, 9.88 mmol) in MeOH (30 mL) NaOMe (1 M) was added. The mixture was neutralized with AcOH after 1 h and concentrated. The dry residue was dissolved in pyridine (15 mL) and tert-butyldimethylsilyl chloride (1.94 g, 12.87 mmol) was added. The reaction mixture was stirred at rt overnight. Acetylation with acetic anhydride, dilution with toluene, filtration (silica), concentration and purification by chromatography (1:0→1:1 toluene-EtOAc) gave 23 (4.357 g, 9.73 mmol, 99%); [α]D+109° (c 1.0, CHCl3); 13C NMR δ −5.33, −5.28 (CH3Si), 14.7 (SCH2CH3), 18.4 ((CH3)3CSi), 20.7, 20.9 (CH3CO), 25.0 (SCH2CH3), 25.9 ((CH3)3CSi), 62.6, 62.9, 67.0, 71.7, 71.9 (C-2-6), 81.5 (C-1), 169.7, 170.1 (CH3CO); 1H NMR δ 0.05 (s, 3H), 0.05 (s, 3H), 0.90 (s, 9H), 1.30 (t, 3H), 2.05 (s, 3H), 2.10 (s, 3H), 2.55-2.75 (m, 2H), 3.60-3.75 (m, 2H), 4.10 (m, 1H), 4.15-4.20 (m, 1H), 5.20-5.25 (m, 1H), 5.30-5.35 (m, 1H); HRMS calcd for C18H33N3NaO6SSi [M+Na]+ 470.1757, found 470.1750.

Workup

  1. concentrationconcentrated
  2. dissolutionThe dry residue was dissolved in pyridine (15 mL)
  3. filtrationAcetylation with acetic anhydride, dilution with toluene, filtration (silica), concentration and purification by chromatography (1:0→1:1 toluene-EtOAc)

Sources & evidence

ORD record
ord-ff2f291cc69c46bdb1f58b6b3a627bbe
Source dataset
uspto-grants-2011_11
Patent number
US08062641B2

Reaction notes

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